Acidic activator supports and catalysts for olefin polymerization

ABSTRACT

This invention relates to the field of olefin polymerization catalyst compositions, and methods for the polymerization and copolymerization of olefins, typically using a supported catalyst composition. In one aspect, this invention encompasses precontacting a metallocene with an olefin or alkyne monomer and an organoaluminum compound, prior to contacting this mixture with the acidic activator-support.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of co-pending U.S. patentapplication Ser. No. 10/877,039, filed on Jun. 24, 2004, now U.S. Pat.No. ______, which is incorporated herein by reference in its entirety.

TECHNICAL FIELD OF THE INVENTION

This invention relates to the field of olefin polymerization catalystcompositions, methods for the polymerization of olefins, and olefinpolymers.

BACKGROUND OF THE INVENTION

It is known that mono-1-olefins (α-olefins), including ethylene, can bepolymerized with catalyst compositions employing titanium, zirconium,vanadium, chromium or other metals, impregnated on a variety of supportmaterials, often in the presence of cocatalysts. These catalystcompositions may be useful for both homopolymerization of ethylene, aswell as copolymerization of ethylene with comonomers such as propylene,1-butene, 1-hexene, or other higher α-olefins. Therefore, there exists aconstant search to develop new olefin polymerization catalysts, catalystactivation processes, and methods of making and using catalysts thatwill provide enhanced catalytic activities and polymeric materialstailored to specific end uses.

One type of catalyst system comprises organometal compounds,particularly metallocene compounds. It is known that contacting waterwith trimethylaluminum under appropriate conditions forms methylaluminoxane, and subsequently contacting methyl aluminoxane with ametallocene compound forms a metallocene polymerization catalyst.However, in order to achieve the desired high polymerization activities,large amounts of methyl aluminoxane, and hence large amounts ofexpensive trimethylaluminum, are necessary to form the activemetallocene catalysts. This feature has been an impediment to thecommercialization of metallocene catalyst systems, thereforeimprovements in catalyst compositions and in methods of making thecatalyst are needed to afford the desired high polymerizationactivities.

What are needed are new catalyst compositions and methods of making thecatalyst compositions that afford high polymerization activities, andwill allow polymer properties to be maintained within the desiredspecification ranges. One method to achieve this goal is to develop newpolymerization methods that provide and utilize catalysts ofsufficiently high activity as to be commercially viable.

SUMMARY OF THE INVENTION

This invention comprises catalyst compositions, methods for preparingcatalyst compositions, and methods for polymerizing olefins andacetylenes using the catalyst compositions. In the course of examiningmetallocene olefin polymerization catalysts, it was discovered thatincreased activity in metallocene catalyst compositions could beachieved by precontacting the metallocene compound with an alkene oralkyne monomer and an organoaluminum cocatalyst for some period of timebefore the mixture is contacted with an acidic activator-support.

The mixture of at least one metallocene, alkene or alkyne monomer, andorganoaluminum cocatalyst compound, before it is contacted with theactivator-support, is termed the “precontacted” mixture. The mixture ofmetallocene, monomer, organoaluminum cocatalyst, and activator-support,formed from contacting the precontacted mixture with the acidicactivator-support, is termed the “postcontacted” mixture. Thisterminology is used regardless of what type of reaction occurs betweencomponents of the mixtures. For example, according to this description,it is possible for the precontacted organoaluminum compound, once it isadmixed with the metallocene or metallocenes and the olefin or alkynemonomer, to have a different chemical formulation and structure from thedistinct organoaluminum compound used to prepare the precontactedmixture. Accordingly, the metallocene, the organoaluminum compound, theolefin or alkyne, and the acidic activator-support, whether precontactedor postcontacted, are described according to the correspondingmetallocene, organoaluminum compound, olefin or alkyne, and acidicactivator-support used to contact the other components in preparing theprecontacted or postcontacted mixtures.

Therefore, in one aspect, the catalyst composition of this inventioncomprises: at least one precontacted metallocene; at least oneprecontacted organoaluminum compound; at least one precontacted olefinor alkyne; and at least one postcontacted acidic activator-support.

In another aspect, the precontacted metallocene comprises a compoundhaving the following formula:(X¹)(X²)(X³)(X⁴)M¹,

wherein M¹ is selected from titanium, zirconium, or hafnium;

wherein (X¹) is independently selected from cyclopentadienyl, indenyl,fluorenyl, boratabenzene, substituted cyclopentadienyl, substitutedindenyl, substituted fluorenyl, or substituted boratabenzene;

wherein each substituent on the substituted cyclopentadienyl,substituted indenyl, substituted fluorenyl or substituted boratabenzeneof (X¹) is independently selected from an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, a germanium group, a tingroup, a lead group, a boron group, an aluminum group, an inorganicgroup, an organometallic group, or a substituted derivative thereof, anyone of which having from 1 to about 20 carbon atoms; a halide; orhydrogen;

wherein at least one substituent on (X¹) is optionally a bridging groupthat connects (X¹) and (X²);

wherein (X³) and (X⁴) are independently selected from an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, agermanium group, a tin group, a lead group, a boron group, an aluminumgroup, an inorganic group, an organometallic group, or a substitutedderivative thereof, any one of which having from 1 to about 20 carbonatoms; or a halide.

wherein (X²) is independently selected from a cyclopentadienyl group, anindenyl group, a fluorenyl group, a boratabenzene group, an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, agermanium group, a tin group, a lead group, a boron group, an aluminumgroup, an inorganic group, an organometallic group, or a substitutedderivative thereof, any one of which having from 1 to about 20 carbonatoms; or a halide;

wherein each substituent on the substituted (X²) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; and

wherein at least one substituent on (X²) is optionally a bridging groupthat connects (X¹) and (X²).

In another aspect of this invention, the precontacted organoaluminumcompound comprises an organoaluminum compound with the followingformula:Al(X⁵)_(n)(X⁶)_(3−n),wherein (X⁵) is a hydrocarbyl having from 2 to about 20 carbon atoms;(X⁶) is selected from alkoxide or aryloxide, any one of which havingfrom 1 to about 20 carbon atoms, halide, or hydride; and n is a numberfrom 1 to 3, inclusive.

In still another aspect of the invention, the precontacted olefin oralkyne comprises a compound having from 2 to about 30 carbon atoms permolecule and having at least one carbon-carbon double bond or at leastone carbon-carbon triple bond.

Yet another aspect of this invention is the postcontacted acidicactivator-support which comprises a solid oxide treated with anelectron-withdrawing anion, wherein:

the solid oxide is selected from silica, alumina, silica-alumina,aluminum phosphate, heteropolytungstates, titania, zirconia, magnesia,boria, zinc oxide, mixed oxides thereof, or mixtures thereof; and

the electron-withdrawing anion is selected from fluoride, chloride,bromide, phosphate, triflate, bisulfate, sulfate, or any combinationthereof.

In one aspect of this invention, for example, the metallocene compoundcomprises a zirconium metallocene such as bis(indenyl)zirconiumdichloride (Ind₂ZrCl₂) or bis(cyclopentadienyl)zirconium dichloride(Cp₂ZrCl₂), which is employed along with triethylaluminum cocatalyst anda fluoride-treated silica-alumina acidic activator-support. Theactivator-support of this invention, of which fluorided silica-aluminais one example, exhibits enhanced acidity as compared to thecorresponding untreated solid oxide compound. The activator-support alsofunctions as a catalyst activator as compared to the correspondinguntreated solid oxide. Accordingly, the acidic activator-supportfunctions as an “activator” because it is not merely an inert supportcomponent of the catalyst composition, but is involved in effecting theobserved catalytic chemistry.

In another aspect of this invention, for example, precontacting ametallocene compound with 1-hexene and triethylaluminum, typically forat least about 10 minutes, prior to contacting this mixture with theacidic activator-support such as fluorided silica-alumina, theproductivity of the subsequent olefin polymerization was increased byseveral-fold as compared to a catalyst composition using the samecomponents, but without a precontacting step. The enhanced activitycatalyst composition of this invention can be used forhomopolymerization of an α-olefin monomer, for copolymerization of anα-olefin and a comonomer, and for polymerization of alkynes as well.

This invention also comprises methods of making catalyst compositionsthat utilize at least one metallocene catalyst, at least oneorganoaluminum compound as cocatalysts, and an acidic activator-support.The methods of this invention comprise precontacting the metallocenecatalyst and an organoaluminum cocatalyst with an olefin or alkynecompound typically, but not necessarily, a monomer to be polymerized orcopolymerized, prior to contacting this precontacted mixture with theacidic activator-support. Such methods allow for, among other things,attaining a high polymerization activity and productivity.

Thus, in one aspect, this invention provides a process to produce acatalyst composition, comprising:

-   -   contacting at least one metallocene, at least one organoaluminum        compound, and at least one olefin or alkyne for a first period        of time to form a precontacted mixture comprising at least one        precontacted metallocene, at least one precontacted        organoaluminum compound, and at least one precontacted olefin or        alkyne; and    -   contacting the precontacted mixture with at least one acidic        activator-support for a second period of time to form a        postcontacted mixture comprising at least one postcontacted        metallocene, at least one postcontacted organoaluminum compound,        at least one postcontacted olefin or alkyne, and at least one        postcontacted acidic activator-support.

Further, this invention encompasses a catalyst composition thatcomprises cyclic organoaluminum compounds, particularlyaluminacyclopentanes, that derive from precontacting an organoaluminumcocatalyst with an unsaturated compound. This invention also comprises amethod of preparing a catalyst composition which generates cyclicorganoaluminum compounds from precontacting an organoaluminum cocatalystwith an unsaturated compound.

The present invention further comprises new catalyst compositions,methods for preparing catalyst compositions, and methods forpolymerizing olefins or alkynes that result in improved productivity,without the need for using large excess concentrations of expensiveorganoaluminum cocatalysts.

Additionally, this invention encompasses a process comprising contactingat least one monomer and the catalyst composition under polymerizationconditions to produce the polymer. Thus, this invention comprisesmethods for polymerizing olefins and alkynes using the catalystcompositions prepared as described herein.

This invention also comprises an article that comprises the polymerproduced with the catalyst composition of this invention.

These and other features, aspects, embodiments, and advantages of thepresent invention will become apparent after a review of the followingdetailed description of the disclosed features.

The following patent applications, filed contemporaneously with thepresent application, are incorporated by reference herein in theirentireties: U.S. patent application Ser. No. 10/876,891; U.S. patentapplication Ser. No. 10/876,930; U.S. patent application Ser. No.10/876,948, now U.S. Pat. No. 7,064,225; and U.S. patent applicationSer. No. 10/877,021.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides new catalyst compositions, methods forpreparing catalyst compositions, and methods for using the catalystcompositions to polymerize olefins and acetylenes. In one aspect, thecatalyst composition of this invention comprises: at least oneprecontacted metallocene; at least one precontacted organoaluminumcompound; at least one precontacted olefin or alkyne; and at least onepostcontacted acidic activator-support.

In yet another aspect, the present invention provides a catalystcomposition comprising an optional cocatalyst in addition to theprecontacted metallocene, precontacted organoaluminum compound,precontacted olefin or alkyne, and postcontacted acidicactivator-support. In one aspect, the optional cocatalyst may beselected from at least one aluminoxane, at least one organoboroncompound, at least one ionizing ionic compound, or any combinationthereof. In another aspect, the optional cocatalyst may be used in theprecontacting step, in the postcontacting step, or in both steps.Further, any combination of cocatalysts may be used in either step, orin both steps.

In still another aspect, this invention provides a process to produce acatalyst composition, comprising:

-   -   contacting a metallocene, an organoaluminum compound, and an        olefin or alkyne for a first period of time to form a        precontacted mixture comprising a precontacted metallocene, a        precontacted organoaluminum compound, and a precontacted olefin        or ethylene; and    -   contacting the precontacted mixture with a acidic        activator-support for a second period of time to form a        postcontacted mixture comprising a postcontacted metallocene, a        postcontacted organoaluminum compound, a postcontacted olefin or        alkyne, and a postcontacted acidic activator-support.        Catalyst Compositions and Components        The Metallocene Compound

The present invention provides catalyst compositions comprising at leastone metallocene compound, at least one organoaluminum compound, at leastone olefin or alkyne, and at least one acidic activator-support. In oneaspect, the metallocene compound and the organoaluminum compound areprecontacted with the olefin or alkyne to form a precontacted mixture,prior to contacting this precontacted mixture with the acidicactivator-support. The metallocene compound may comprise a metallocenecompound of titanium, zirconium, and hafnium.

In one aspect, the metallocene compound that is used to prepare theprecontacted mixture, comprises a compound having the following formula:(X¹)(X²)(X³)(X⁴)M¹,

wherein M¹ is selected from titanium, zirconium, or hafnium;

wherein (X¹) is independently selected from cyclopentadienyl, indenyl,fluorenyl, boratabenzene, substituted cyclopentadienyl, substitutedindenyl, substituted fluorenyl, or substituted boratabenzene;

wherein each substituent on the substituted cyclopentadienyl,substituted indenyl, substituted fluorenyl or substituted boratabenzeneof (X¹) is independently selected from an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, a germanium group, a tingroup, a lead group, a boron group, an aluminum group, an inorganicgroup, an organometallic group, or a substituted derivative thereof, anyone of which having from 1 to about 20 carbon atoms; a halide; orhydrogen;

wherein at least one substituent on (X¹) is optionally a bridging groupthat connects (X¹) and (X²);

wherein (X³) and (X⁴) are independently selected from an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, agermanium group, a tin group, a lead group, a boron group, an aluminumgroup, an inorganic group, an organometallic group, or a substitutedderivative thereof, any one of which having from 1 to about 20 carbonatoms; or a halide.

wherein (X²) is independently selected from a cyclopentadienyl group, anindenyl group, a fluorenyl group, a boratabenzene group, an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, agermanium group, a tin group, a lead group, a boron group, an aluminumgroup, an inorganic group, an organometallic group, or a substitutedderivative thereof, any one of which having from 1 to about 20 carbonatoms; or a halide;

wherein each substituent on the substituted (X²) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; and

wherein at least one substituent on (X²) is optionally a bridging groupthat connects (X¹) and (X²).

In one aspect, the following groups may be independently selected assubstituents on (X¹) and (X²), or may be independently selected as the(X²), (X³), or (X⁴) ligand themselves: an aliphatic group, an aromaticgroup, a cyclic group, a combination of aliphatic and cyclic groups, anoxygen group, a sulfur group, a nitrogen group, a phosphorus group, anarsenic group, a carbon group, a silicon group, a germanium group, a tingroup, a lead group, a boron group, an aluminum group, an inorganicgroup, an organometallic group, or a substituted derivative thereof, anyone of which having from 1 to about 20 carbon atoms; or a halide; aslong as these groups do not terminate the activity of the catalystcomposition. This list includes substituents that may be characterizedin more than one of these categories such as benzyl. Further, hydrogenmay be selected as a substituent on (X¹) and (X²), as long as thisgroups do not terminate the activity of the catalyst composition,therefore the notion of a substituted indenyl and substituted fluorenylincludes partially saturated indenyls and fluorenyls including, but notlimited to, tetrahydroindenyls, tetrahydrofluorenyls, andoctahydrofluorenyls.

Examples of each of these groups include, but are not limited to, thefollowing groups. In each example presented below, unless otherwisespecified, R is independently selected from: an aliphatic group; anaromatic group; a cyclic group; any combination thereof; any substitutedderivative thereof, including but not limited to, a halide-, analkoxide-, or an amide-substituted derivative thereof; any one of whichhas from 1 to about 20 carbon atoms; or hydrogen. Also included in thesegroups are any unsubstituted, branched, or linear analogs thereof.

Examples of aliphatic groups, in each instance, include, but are notlimited to, an alkyl group, a cycloalkyl group, an alkenyl group, acycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclicaliphatic group, and the like, and includes all substituted,unsubstituted, branched, and linear analogs or derivatives thereof, ineach instance having from one to about 20 carbon atoms. Thus, aliphaticgroups include, but are not limited to, hydrocarbyls such as paraffinsand alkenyls. For example, aliphatic groups as used herein includemethyl, ethyl, propyl, n-butyl, tert-butyl, sec-butyl, isobutyl, amyl,isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl,2-ethylhexyl, pentenyl, butenyl, and the like.

Examples of aromatic groups, in each instance, include, but are notlimited to, phenyl, naphthyl, anthacenyl, and the like, includingsubstituted derivatives thereof, in each instance having from 6 to about25 carbons. Substituted derivatives of aromatic compounds include, butare not limited to, tolyl, xylyl, mesityl, and the like, including anyheteroatom substituted derivative thereof.

Examples of cyclic groups, in each instance, include, but are notlimited to, cycloparaffins, cycloolefins, cycloalkynes, aryl groups suchas phenyl, bicyclic groups and the like, including substitutedderivatives thereof, in each instance having from about 3 to about 20carbon atoms. Thus heteroatom-substituted cyclic groups such as furanylare included herein. Also included herein are cyclic hydrocarbyl groupssuch as aryl, cycloalkyl, cycloalkenyl, cycloalkadienyl, aralkyl,aralkenyl, aralkynyl, and the like.

In each instance, aliphatic and cyclic groups are groups comprising analiphatic portion and a cyclic portion, examples of which include, butare not limited to, groups such as: —(CH₂)_(m)C₆H_(q)R_(5−q) wherein mis an integer from 1 to about 10, q is an integer from 1 to 5,inclusive; (CH₂)_(m)C₆H_(q)R_(10−q) wherein m is an integer from 1 toabout 10, q is an integer from 1 to 10, inclusive; and(CH₂)_(m)C₅H_(q)R_(9−q) wherein m is an integer from 1 to about 10, q isan integer from 1 to 9, inclusive. In each instance and as definedabove, R is independently selected from: an aliphatic group; an aromaticgroup; a cyclic group; any combination thereof; any substitutedderivative thereof, including but not limited to, a halide-, analkoxide-, or an amide-substituted derivative thereof; any one of whichhas from 1 to about 20 carbon atoms; or hydrogen. In one aspect,aliphatic and cyclic groups include, but are not limited to: —CH₂C₆H₅;—CH₂C₆H₄F; —CH₂C₆H₄Cl; —CH₂C₆H₄Br; —CH₂C₆H₄I; —CH₂C₆H₄OMe; —CH₂C₆H₄OEt;—CH₂C₆H₄NH₂; —CH₂C₆H₄NMe₂; —CH₂C₆H₄NEt₂; —CH₂CH₂C₆H₅; —CH₂CH₂C₆H₄F;—CH₂CH₂C₆H₄Cl; —CH₂CH₂C₆H₄Br; —CH₂CH₂C₆H₄I; —CH₂CH₂C₆H₄OMe;—CH₂CH₂C₆H₄OEt; —CH₂CH₂C₆H₄NH₂; —CH₂CH₂C₆H₄NMe₂; —CH₂CH₂C₆H₄NEt₂; anyregioisomer thereof, and any substituted derivative thereof.

Examples of halides, in each instance, include fluoride, chloride,bromide, and iodide.

In each instance, oxygen groups are oxygen-containing groups, examplesof which include, but are not limited to, alkoxy or aryloxy groups(—OR), —OC(O)R, —OC(O)H, —OSiR₃, —OPR₂, —OAlR₂, and the like, includingsubstituted derivatives thereof, wherein R in each instance is selectedfrom alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substitutedaryl, or substituted aralkyl having from 1 to about 20 carbon atoms.Examples of alkoxy or aryloxy groups (—OR) groups include, but are notlimited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substitutedphenoxy, and the like.

In each instance, sulfur groups are sulfur-containing groups, examplesof which include, but are not limited to, —SR, —OSO₂R, —OSO₂OR, —SCN,—SO₂R, and the like, including substituted derivatives thereof, whereinR in each instance is selected from alkyl, cycloalkyl, aryl, aralkyl,substituted alkyl, substituted aryl, or substituted aralkyl having from1 to about 20 carbon atoms.

In each instance, nitrogen groups are nitrogen-containing groups, whichinclude, but are not limited to, —NH₂, —NHR, —NR₂, —NO₂, —N₃, and thelike, including substituted derivatives thereof, wherein R in eachinstance is selected from alkyl, cycloalkyl, aryl, aralkyl, substitutedalkyl, substituted aryl, or substituted aralkyl having from 1 to about20 carbon atoms.

In each instance, phosphorus groups are phosphorus-containing groups,which include, but are not limited to, —PH₂, —PHR, —PR₂, —P(O)R₂,—P(OR)₂, —P(O)(OR)₂, and the like, including substituted derivativesthereof, wherein R in each instance is selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl having from 1 to about 20 carbon atoms.

In each instance, arsenic groups are arsenic-containing groups, whichinclude, but are not limited to, —AsHR, —AsR₂, —As(O)R₂, —As(OR)₂,—As(O)(OR)₂, and the like, including substituted derivatives thereof,wherein R in each instance is selected from alkyl, cycloalkyl, aryl,aralkyl, substituted alkyl, substituted aryl, or substituted aralkylhaving from 1 to about 20 carbon atoms.

In each instance, carbon groups are carbon-containing groups, whichinclude, but are not limited to, alkyl halide groups that comprisehalide-substituted alkyl groups with 1 to about 20 carbon atoms, aralkylgroups with 1 to about 20 carbon atoms, —C(O)H, —C(O)R, —C(O)OR, cyano,—C(NR)H, —C(NR)R, —C(NR)OR, and the like, including substitutedderivatives thereof, wherein R in each instance is selected from alkyl,cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, orsubstituted aralkyl having from 1 to about 20 carbon atoms.

In each instance, silicon groups are silicon-containing groups, whichinclude, but are not limited to, silyl groups such alkylsilyl groups,arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like,which in each instance have from 1 to about 20 carbon atoms. Forexample, silicon groups include trimethylsilyl and phenyloctylsilylgroups.

In each instance, germanium groups are germanium-containing groups,which include, but are not limited to, germyl groups such alkylgermylgroups, arylgermyl groups, arylalkylgermyl groups, germyloxy groups, andthe like, which in each instance have from 1 to about 20 carbon atoms.

In each instance, tin groups are tin-containing groups, which include,but are not limited to, stannyl groups such alkylstannyl groups,arylstannyl groups, arylalkylstannyl groups, stannoxy (or “stannyloxy”)groups, and the like, which in each instance have from 1 to about 20carbon atoms. Thus, tin groups include, but are not limited to, stannoxygroups.

In each instance, lead groups are lead-containing groups, which include,but are not limited to, alkyllead groups, aryllead groups, arylalkylleadgroups, and the like, which in each instance, have from 1 to about 20carbon atoms.

In each instance, boron groups are boron-containing groups, whichinclude, but are not limited to, —BR₂, —BX₂, —BRX, wherein X is amonoanionic group such as halide, hydride, alkoxide, alkyl thiolate, andthe like, and wherein R in each instance is selected from alkyl,cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, orsubstituted aralkyl having from 1 to about 20 carbon atoms.

In each instance, aluminum groups are aluminum-containing groups, whichinclude, but are not limited to, —AlR₂, —AlX₂, —AlRX, wherein X is amonoanionic group such as halide, hydride, alkoxide, alkyl thiolate, andthe like, and wherein R in each instance is selected from alkyl,cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, orsubstituted aralkyl having from 1 to about 20 carbon atoms.

Examples of inorganic groups that may be used as substituents forsubstituted cyclopentadienyls, substituted indenyls, substitutedfluorenyls, and substituted boratabenzenes, in each instance, include,but are not limited to, —SO₂X, —OAlX₂, —OSiX₃, —OPX₂, —SX, —OSO₂X,—AsX₂, —As(O)X₂, —PX₂, and the like, wherein X is a monoanionic groupsuch as halide, hydride, amide, alkoxide, alkyl thiolate, and the like,and wherein any alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl group or substituent on theseligands has from 1 to about 20 carbon atoms.

Examples of organometallic groups that may be used as substituents forsubstituted cyclopentadienyls, substituted indenyls, and substitutedfluorenyls, in each instance, include, but are not limited to,organoboron groups, organoaluminum groups, organogallium groups,organosilicon groups, organogermanium groups, organotin groups,organolead groups, organo-transition metal groups, and the like, havingfrom 1 to about 20 carbon atoms.

In one aspect of this invention, (X³) and (X⁴) are selected from halidesor hydrocarbyls having from 1 to about 10 carbon atoms. More typically,(X³) and (X⁴) are selected from fluoro, chloro, or methyl.

In another aspect, because of the selections possible for (X¹) and (X²),the metallocene of this invention can comprise amonokis(cyclopentadienyl) compound, a bis(cyclopentadienyl) compound, amonokis(indenyl) compound, a bis(indenyl) compound, a monokis(fluorenyl)compound, a bis(fluorenyl) compound, a (cyclopentadienyl)(indenyl)compound, a (cyclopentadienyl)-(fluorenyl) compound, an(indenyl)(fluorenyl) compound, substituted analogs thereof, bridgedanalogs thereof, and the like. Thus, at least one substituent on (X²) isoptionally a bridging group that connects (X¹) and (X²).

In one aspect of the invention, (X¹) is independently selected fromcyclopentadienyl, indenyl, fluorenyl, boratabenzene, substitutedcyclopentadienyl, substituted indenyl, substituted fluorenyl, orsubstituted boratabenzene; and (X²) is independently selected from acyclopentadienyl group, an indenyl group, a fluorenyl group, aboratabenzene group, an aliphatic group, an aromatic group, a cyclicgroup, a combination of aliphatic and cyclic groups, an oxygen group, asulfur group, a nitrogen group, a phosphorus group, an arsenic group, acarbon group, a silicon group, a germanium group, a tin group, a leadgroup, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide; as long asthese groups do not terminate the activity of the catalyst composition.

At least one substituent on (X¹) or (X²) may optionally be a bridginggroup that connects or bridges the (X¹) and (X²) ligands, as long as thebridging group does not terminate the activity of the catalystcomposition. The linkage that connects (X¹) and (X²), that is, theshortest link of the bridging moiety, can be a single atom selected fromcarbon, silicon, germanium, or tin atom. In one aspect, the bridgingatom is a carbon or silicon atom, in which case the bridge comprises asubstituted methylene (or methylidene) group or a substituted silylenegroup. In another aspect, the linkage that connects (X¹) and (X²), thatis, the shortest link of the bridging moiety, can be from 2 to about 4atoms. In yet another aspect, the linkage that connects (X¹) and (X²),that is, the shortest link of the bridging moiety, can comprise from 2to about 4 carbon atoms.

In another aspect, examples of bridging groups include, but are notlimited to, aliphatic groups, cyclic groups, combinations of aliphaticgroups and cyclic groups, phosphorous groups, nitrogen groups,organometallic groups, silicon, phosphorus, boron, germanium, and thelike. Examples of aliphatic groups that can serve as bridges between(X¹) and (X²) include, but are not limited to, hydrocarbyls, such asparaffins and olefins. Examples of cyclic groups that can serve asbridges between (X¹) and (X²) include, bur are not limited to,cycloparaffins, cycloolefins, cycloalkynes, arenes, and the like.Examples of organometallic groups that can serve as bridges between (X¹)and (X²) include, but are not limited to, substituted silyl derivatives,substituted tin groups, substituted germanium groups, substituted borongroups, and the like.

In another aspect, the optional bridging group may be substituted by atleast one substituent, wherein the substituent may be independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen.

Numerous processes to prepare organometal compounds that can be employedin this invention, particularly metallocenes, have been reported. Forexample, U.S. Pat. Nos. 4,939,217, 5,210,352, 5,436,305, 5,401,817,5,631,335, 5,571,880, 5,191,132, 5,399,636, 5,565,592, 5,347,026,5,594,078, 5,498,581, 5,496,781, 5,563,284, 5,554,795, 5,420,320,5,451,649, 5,541,272, 5,705,578, 5,631,203, 5,654,454, 5,705,579, and5,668,230 describe such methods, each of which is incorporated byreference herein, in its entirety. Other processes to preparemetallocene compounds that can be employed in this invention have beenreported in references such as: Köppl, A. Alt, H. G. J. Mol. Catal. A.2001, 165, 23; Kajigaeshi, S.; Kadowaki, T.; Nishida, A.; Fujisaki, S.The Chemical Society of Japan, 1986, 59, 97; Alt, H. G.; Jung, M.; Kehr,G. J. Organomet. Chem. 1998, 562, 153-181; and Alt, H. G.; Jung, M. J.Organomet. Chem. 1998, 568, 87-112; each of which is incorporated byreference herein, in its entirety. Further, additional processes toprepare metallocene compounds that can be employed in this inventionhave been reported in: Journal of Organometallic Chemistry, 1996, 522,39-54, which is incorporated by reference herein, in its entirety. Thefollowing treatises also describe such methods: Wailes, P. C.; Coutts,R. S. P.; Weigold, H. in Organometallic Chemistry of Titanium,Zirconium, and Hafnium, Academic; New York, 1974.; Cardin, D. J.;Lappert, M. F.; and Raston, C. L.; Chemistry of Organo-Zirconium and-Hafnium Compounds; Halstead Press; New York, 1986; each of which isincorporated by reference herein, in its entirety.

In one aspect of this invention, the metallocene compounds of thepresent invention include, but are not limited to the followingcompounds:

bis(cyclopentadienyl)hafnium dichloride,

bis(cyclopentadienyl)zirconium dichloride,

1,2-ethanediylbis(η⁵-1-indenyl)di-n-butoxyhafnium,

1,2-ethanediylbis(η⁵-1-indenyl)dimethylzirconium,

3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride,

methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride,

bis(n-butylcyclopentadienyl)bis(t-butylamido)hafnium,

bis(1-n-butyl-3-methyl-cyclopentadienyl)zirconium dichloride;

bis(n-butylcyclopentadienyl)zirconium dichloride,

dimethylsilylbis(1-indenyl)zirconium dichloride,

octyl(phenyl)silylbis(1-indenyl)hafnium dichloride,

dimethylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride,

dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride,

1,2-ethanediylbis(9-fluorenyl)zirconium dichloride,

indenyl diethoxy titanium(IV) chloride,

(isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride,

bis(pentamethylcyclopentadienyl)zirconium dichloride,

bis(indenyl)zirconium dichloride,

methyl(octyl)silylbis(9-fluorenyl)zirconium dichloride,

bis(2,7-di-tert-butylfluorenyl)-ethan-1,2-diyl)zirconium(IV) dichloride,

bis-[1-(N,N-diisopropylamino)boratabenzene]hydridozirconiumtrifluoromethylsulfonate,

methyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride, [(η⁵-C₅H₄)CCH₃(CH₂CH₂CH═CH₂)(η⁵-9-C₁₃H₉)]ZrCl₂;

methyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride, [(η⁵-C₅H₄)CCH₃(CH₂CH₂CH═CH₂)(η⁵-9-C₁₃H₇-2,7-^(t)Bu₂)]ZrCl₂;

methyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride, [(η⁵-C₅H₄)CCH₃(CH₂CH₂CH₂CH═CH₂)(η⁵-9-C₁₃H₉)]ZrCl₂;

methyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,[(η⁵-C₅H₄)CCH₃(CH₂CH₂CH₂CH═CH₂)(η⁵-9-C₁₃H₇-2,7-^(t)Bu₂)]ZrCl₂;

phenyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride, [(η⁵-C₅H₄)C(C₆H₅)(CH₂CH₂CH═CH₂)(η⁵-9-C₁₃H₉)]ZrCl₂;

phenyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,[(η⁵-C₅H₄)C(C₆H₅)(CH₂CH₂CH═CH₂)(η⁵-9-C₁₃H₇-2,7-^(t)Bu₂)]ZrCl₂;

phenyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride, [(η⁵-C₅H₄)C(C₆H₅)(CH₂CH₂CH₂CH═CH₂)(η⁵-9-C₁₃H₉)]ZrCl₂;

phenyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,[(η⁵-C₅H₄)C(C₆H₅)(CH₂CH₂CH₂CH═CH₂)(η⁵-9-C₁₃H₇-2,7-^(t)Bu₂)]ZrCl₂; andthe like.

In yet another aspect of this invention, examples of the metallocenethat are useful in the catalyst composition of this invention include acompound with the formula I:

wherein E is selected from C, Si, Ge, or Sn; R1 is selected from H or ahydrocarbyl group having from 1 to about 12 carbon atoms; R2 is selectedfrom an alkenyl group having from about 3 to about 12 carbon atoms; andR3 is selected from H or a hydrocarbyl group having from 1 to about 12carbon atoms.

In another aspect, the catalyst composition of this invention comprisesa metallocene compound described by structure II as follows:

wherein R1 is selected from methyl or phenyl; R2 is selected from3-butenyl (—CH₂CH₂CH═CH₂) or 4-pentenyl (—CH₂CH₂CH₂CH═CH₂); and R3 isselected from H or t-butyl.

Typically, the organometal compound comprisesbis(n-butylcyclopentadienyl)zirconium dichloride; bis(indenyl)zirconiumdichloride; dimethylsilylbis(1-indenyl)zirconium dichloride;methyloctylsilylbis(9-fluorenyl)zirconium dichloride; orbis(2,7-di-tert-butylfluorenyl)-ethan-1,2-diyl)zirconium (IV)dichloride.

The Organoaluminum Compound

In one aspect, the present invention provides catalyst compositionscomprising at least one metallocene compound, at least oneorganoaluminum compound, at least one olefin or alkyne, and at least oneacidic activator-support. In another one aspect, the metallocenecompound and the organoaluminum compound are precontacted with theolefin or alkyne to form a precontacted mixture, prior to contactingthis precontacted mixture with the acidic activator-support. Typically,a portion of the organoaluminum compound is added to the precontactedmixture and another portion of the organoaluminum compound is added tothe postcontacted mixture, although all the organoaluminum compound maybe used to prepare the catalyst in the precontacting step.

In another aspect of this invention, the precontacted mixture cancomprise a first organoaluminum compound in addition to at least onemetallocene and an olefin or acetylene monomer, and the postcontactedmixture can comprise a second organoaluminum compound in addition to theprecontacted mixture and the acidic activator-support. The secondorganoaluminum compound can be the same or different from the firstorganoaluminum compound. Specifically, any of the possible firstorganoaluminum compounds may also be used as choices for the secondorganoaluminum compound, however not all of the possible secondorganoaluminum compounds work well as choices for the firstorganoaluminum compound for use in the precontacted mixture.

In yet another aspect, the first organoaluminum compound that can beused in this invention in the precontacted mixture with the metallocenecompound and an olefin or alkyne monomer includes, but is not limitedto, a compound having the following general formula:Al(X⁵)_(n)(X⁶)_(3−n),wherein (X⁵) is a hydrocarbyl having from 2 to about 20 carbon atoms,and (X⁶) is selected from alkoxide or aryloxide, any one of which havingfrom 1 to about 20 carbon atoms, halide, or hydride; and n is a numberfrom 1 to 3, inclusive. In one aspect, (X⁵) is an alkyl having from 2 toabout 10 carbon atoms, and in another aspect, (X⁵) is selected fromethyl, propyl, n-butyl, sec-butyl, isobutyl, hexyl, and the like.

The substituent (X⁶) in the formula for the first organoaluminumcompound is selected from alkoxide or aryloxide, any one of which havingfrom 1 to about 20 carbon atoms, halide, or hydride. In one aspect, (X⁶)is independently selected from fluoro or chloro, and in another aspect,(X⁶) is chloro.

In the formula Al(X⁵)_(n)(X⁶)_(3−n), for the first organoaluminumcompound, n is a number from 1 to 3 inclusive, and typically, n is 3.The value of n is not restricted to be an integer, therefore thisformula includes sesquihalide compounds.

In yet another aspect, the second organoaluminum compound that can beused in the postcontacted mixture, that is, in the subsequent contactingof the precontacted components with additional organoaluminum compoundand the activator-support, includes, but is not limited to, a compoundhaving the following general formula:Al(X⁵)_(n)(X⁶)_(3−n),wherein (X⁵) is a hydrocarbyl having from 1 to about 20 carbon atoms,and (X⁶) is selected from alkoxide or aryloxide, any one of which havingfrom 1 to about 20 carbon atoms, halide, or hydride; and n is a numberfrom 1 to 3, inclusive. In one aspect, (X⁵) is an alkyl having from 1 toabout 10 carbon atoms, and in another aspect, (X⁵) is selected frommethyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, hexyl, and thelike.

The substituent (X⁶) in the formula for the second organoaluminumcompound is selected from alkoxide or aryloxide, any one of which havingfrom 1 to about 20 carbon atoms, halide, or hydride. In one aspect, (X⁶)is independently selected from fluoro or chloro, and in another aspect,(X⁶) is chloro.

In the second organoaluminum compound formula Al(X⁵)_(n)(X⁶)_(3−n), n isa number from 1 to 3 inclusive, and typically, n is 3. The value of n isnot restricted to be an integer, therefore this formula includessesquihalide compounds.

Generally, examples of organoaluminum compounds that can be used in thisinvention include, but are not limited to, trialkylaluminum compounds,dialkylaluminium halide compounds, alkylaluminum dihalide compounds,alkylaluminum sesquihalide compounds, and combinations thereof. Specificexamples of organoaluminum compounds that can be used in this inventionin the precontacted mixture with the organometal compound and an olefinor alkyne monomer include, but are not limited to, triethylaluminum(TEA); tripropylaluminum; diethylaluminum ethoxide; tributylaluminum;diisobutylaluminum hydride; triisobutylaluminum; and diethylaluminumchloride.

When the precontacted mixture comprises a first organoaluminum compoundand the postcontacted mixture comprises a second organoaluminumcompound, any of the possible first organoaluminum compounds may also beused as choices for the second organoaluminum compound. However, not allof the possible second organoaluminum compounds work well for use in theprecontacted mixture. For example, triethyl aluminum (TEA) works well inboth precontacted and postcontacted mixtures, however trimethyl aluminum(TMA) works well only in the postcontacted mixture and not well in theprecontacted mixture. In this example, organoaluminum compounds that canbe used as the second organoaluminum compound in the postcontactedmixture include, but are not limited to, all the compounds that can beused in the precontacted mixture, and further includingtrimethylaluminum (TMA).

The amounts of organoaluminum compound disclosed herein include thetotal amount of organoaluminum compound used in both the precontactedand postcontacted mixtures, and any additional organoaluminum compoundadded to the polymerization reactor. Therefore, total amounts oforganoaluminum compounds are disclosed, regardless of whether a singleorganoaluminum compound is used, or more than one organoaluminumcompound. Triethylaluminum (TEA) is a typical compound used in thisaspect of this invention when only a single organoaluminum compound isemployed.

The Olefin or Acetylene Monomer

In the present invention, at least one organoaluminum compound, at leastone metallocene compound, and at least one olefin or alkyne monomer areprecontacted prior to contacting this mixture with a solid acidicactivator-support, in order to afford an active polymerization catalyst.

Unsaturated reactants that are useful in the precontacting step and inthe polymerization processes with catalyst compositions of thisinvention include olefin compounds having from about 2 to about 30carbon atoms per molecule and having at least one olefinic double bond.This invention encompasses homopolymerization processes using a singleolefin, as well as copolymerization reactions with at least onedifferent olefinic compound. Typically, copolymers of ethylene comprisea major amount of ethylene (>50 mole percent) and a minor amount ofcomonomer <50 mole percent), though this is not a requirement. Thecomonomers that can be copolymerized with ethylene should have fromthree to about 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins may be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalysts of thisinvention include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normaloctenes, the four normal nonenes, the five normal decenes, and mixturesof any two or more thereof. Cyclic and bicyclic olefins, including butnot limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene,and the like, may also be polymerized as described above.

Acetylenes may be also be polymerized according to this invention.Acyclic, cyclic, terminal, internal, linear, branched, substituted,unsubstituted, functionalized, and non-functionalized alkynes may beemployed in this invention. Examples of alkynes that can be polymerizedinclude, but are not limited to, diphenylacetylene, 2-butyne, 2-hexyne,3-hexyne, 2-heptyne, 3-heptyne, 2-octyne, 3-octyne, 4-octyne, and thelike.

In one aspect, when a copolymer is desired, the monomer ethylene may becopolymerized with a comonomer. In another aspect, examples of thecomonomer include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normaloctenes, the four normal nonenes, or the five normal decenes. In anotheraspect, the comonomer may be selected from 1-butene, 1-pentene,1-hexene, 1-octene, 1-decene, or styrene.

In one aspect, the amount of comonomer introduced into a reactor zone toproduce the copolymer is generally from about 0.01 to about 10 weightpercent comonomer based on the total weight of the monomer andcomonomer. In another aspect, the amount of comonomer introduced into areactor zone is from about 0.01 to about 5 weight percent comonomer, andin still another aspect, from about 0.1 to about 4 weight percentcomonomer based on the total weight of the monomer and comonomer.Alternatively, an amount sufficient to give the above describedconcentrations by weight, in the copolymer produced can be used.

While not intending to be bound by this theory, in the event thatbranched, substituted, or functionalized olefins are used as reactants,it is believed that steric hindrance may impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight. In one aspect, at least one reactant for the catalystcompositions of this invention is ethylene, so the polymerizations areeither homopolymerizations or copolymerizations with a differentacyclic, cyclic, terminal, internal, linear, branched, substituted, orunsubstituted olefin. In addition, the catalyst compositions of thisinvention may be used in polymerization of diolefin compounds, includingbut are not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and1,5-hexadiene.

The Solid Acidic Activator-Support

The present invention provides catalyst compositions comprising at leastone metallocene compound, at least one organoaluminum compound, at leastone olefin or alkyne, and at least one acidic activator-support. In oneaspect, the metallocene compound and the organoaluminum compound areprecontacted with the olefin or alkyne to form a precontacted mixture,prior to contacting this precontacted mixture with the acidicactivator-support.

The present invention encompasses catalyst compositions comprising anacidic activator-support, methods for preparing catalyst compositionscomprising an acidic activator-support, and methods for polymerizingolefins and acetylenes using these catalyst compositions. In thisinvention, the metallocene compound may be contacted with an olefinic oracetylenic monomer and an organoaluminum compound for a first period oftime prior to contacting this mixture with the acidic activator-support.Once the precontacted mixture of metallocene, unsaturated monomer, andorganoaluminum compound has been contacted with the acidicactivator-support, this composition which further comprises the acidicactivator-support is termed the “postcontacted” mixture. In one aspect,the postcontacted mixture may be further allowed to remain in contactfor a second period of time prior to being charged into the reactor inwhich the polymerization process will be carried out. In another aspect,the postcontacted mixture may be charged into the reactor immediatelyafter being prepared, or may be prepared directly in the reactor, andthe polymerization reaction initiated immediately thereafter. In thisaspect, the second period of time during which the postcontacted mixtureis allowed to remain in contact is the minimal amount of time requiredto prepare the postcontacted mixture and initiate the polymerizationprocess.

In one aspect, the present invention encompasses catalyst compositionscomprising a chemically-treated solid oxide which serves as an acidicactivator-support, and which is typically used in combination with anorganoaluminum compound. In another aspect, the activator-supportcomprises at least one solid oxide treated with at least oneelectron-withdrawing anion; wherein the solid oxide is selected fromsilica, alumina, silica-alumina, aluminum phosphate,heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide,mixed oxides thereof, or mixtures thereof; and wherein theelectron-withdrawing anion is selected from fluoride, chloride, bromide,phosphate, triflate, bisulfate, sulfate, or any combination thereof.

The activator-support includes the contact product of at least one solidoxide compound and at least one electron-withdrawing anion source. Inone aspect, the solid oxide compound comprises an inorganic oxide. It isnot required that the solid oxide compound be calcined prior tocontacting the electron-withdrawing anion source. The contact productmay be calcined either during or after the solid oxide compound iscontacted with the electron-withdrawing anion source. In this aspect,the solid oxide compound may be calcined or uncalcined. In anotheraspect, the activator-support may comprise the contact product of atleast one calcined solid oxide compound and at least oneelectron-withdrawing anion source.

The activator-support exhibits enhanced acidity as compared to thecorresponding untreated solid oxide compound. The activator-support alsofunctions as a catalyst activator as compared to the correspondinguntreated solid oxide. While not intending to be bound by theory, it isbelieved that the activator-support may function as an ionizing solidoxide compound by completely or partially extracting an anionic ligandfrom the metallocene. However, the activator-support is an activatorregardless of whether it is ionizes the metallocene, abstracts ananionic ligand to form an ion pair, weakens the metal-ligand bond in themetallocene, simply coordinates to an anionic ligand when it contactsthe activator-support, or any other mechanisms by which activation mayoccur. While the activator-support activates the metallocene in theabsence of cocatalysts, it is not necessary to eliminate cocatalystsfrom the catalyst composition. The activation function of theactivator-support is evident in the enhanced activity of catalystcomposition as a whole, as compared to a catalyst composition containingthe corresponding untreated solid oxide. However, it is believed thatthe activator-support functions as an activator, even in the absence ofan organoaluminum compound, aluminoxanes, organoboron compounds, orionizing ionic compounds.

In one aspect, the activator-support of this invention comprises a solidinorganic oxide material, a mixed oxide material, or a combination ofinorganic oxide materials, that is chemically-treated with anelectron-withdrawing component, and optionally treated with a metal.Thus, the solid oxide of this invention encompasses oxide materials suchas alumina, “mixed oxide” compounds thereof such as silica-alumina, andcombinations and mixtures thereof. The mixed oxide compounds such assilica-alumina single chemical phases with more than one metal combinedwith oxygen to form a solid oxide compound, and are encompassed by thisinvention.

In one aspect of this invention, the activator-support further comprisesa metal or metal ion selected from zinc, nickel, vanadium, silver,copper, gallium, tin, tungsten, molybdenum, or any combination thereof.Examples of activator-supports that further comprise a metal or metalion include, but are not limited to, zinc-impregnated chlorided alumina,zinc-impregnated fluorided alumina, zinc-impregnated chloridedsilica-alumina, zinc-impregnated fluorided silica-alumina,zinc-impregnated sulfated alumina, or any combination thereof.

In another aspect, the activator-support of this invention comprises asolid oxide of relatively high porosity, which exhibits Lewis acidic orBrønsted acidic behavior. The solid oxide is chemically-treated with anelectron-withdrawing component, typically an electron-withdrawing anionor an electron-withdrawing anion source, to form a activator-support.While not intending to be bound by the following statement, it isbelieved that treatment of the inorganic oxide with anelectron-withdrawing component augments or enhances the acidity of theoxide. Thus, the activator-support exhibits Lewis or Brønsted aciditywhich is typically greater than the Lewis or Brønsted acidity of theuntreated solid oxide. One method to quantify the acidity of thechemically-treated and untreated solid oxide materials is by comparingthe polymerization activities of the treated and untreated oxides underacid catalyzed reactions. Generally, it is observed that the greater theelectron-withdrawing ability or Lewis acidity of the activator-support,the greater its polymerization activity.

In one aspect, the chemically-treated solid oxide comprises a solidinorganic oxide comprising oxygen and at least one element selected fromGroup 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodictable, or comprising oxygen and at least one element selected from thelanthanide or actinide elements. (See: Hawley's Condensed ChemicalDictionary, 11^(th) Ed., John Wiley & Sons; 1995; Cotton, F. A.;Wilkinson, G.; Murillo; C. A.; and Bochmann; M. Advanced InorganicChemistry, 6^(th) Ed., Wiley-Interscience, 1999.) Usually, the inorganicoxide comprises oxygen and at least one element selected from Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V,W, P, Y, Zn or Zr.

Suitable examples of solid oxide materials or compounds that can be usedin the chemically-treated solid oxide of the present invention include,but are not limited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO,Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO,ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixedoxides thereof, and combinations thereof. Examples of mixed oxides thatcan be used in the activator-support of the present invention include,but are not limited to, silica-alumina, silica-titania, silica-zirconia,zeolites, many clay minerals, alumina-titania, alumina-zirconia, and thelike.

In one aspect of this invention, the solid oxide material ischemically-treated by contacting it with at least oneelectron-withdrawing anion, which may be derived from anyelectron-withdrawing component or an electron-withdrawing anion source.Further, the solid oxide material is optionally chemically-treated witha metal ion, then calcining to form a metal-containing ormetal-impregnated chemically-treated solid oxide. Alternatively, a solidoxide material and an electron-withdrawing anion source are contactedand calcined simultaneously. The method by which the oxide is contactedwith an electron-withdrawing component, typically a salt or an acid ofan electron-withdrawing anion, includes, but is not limited to, gelling,co-gelling, impregnation of one compound onto another, and the like.Typically, following any contacting method, the contacted mixture ofoxide compound, electron-withdrawing anion, and optionally the metal ionis calcined.

The electron-withdrawing component used to treat the oxide is anycomponent that increases the Lewis or Brønsted acidity of the solidoxide upon treatment. In one aspect, the electron-withdrawing componentis an electron-withdrawing anion source compound derived from a salt, anacid, or other compound such as a volatile organic compound that mayserve as a source or precursor for that anion. Examples ofelectron-withdrawing anions and electron-withdrawing anion sourcesinclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, trifluoroacetate, triflate, and the like, includingmixtures and combinations thereof. In addition, other ionic or non-ioniccompounds that serve as sources for these electron-withdrawing anionsmay also be employed in the present invention.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt may beselected from any cation that allows the salt to revert or decomposeback to the acid during calcining. Factors that dictate the suitabilityof the particular salt to serve as a source for the electron-withdrawinganion include, but are not limited to, the solubility of the salt in thedesired solvent, the lack of adverse reactivity of the cation,ion-pairing effects between the cation and anion, hygroscopic propertiesimparted to the salt by the cation, and the like, and thermal stabilityof the anion. Examples of suitable cations in the salt of theelectron-withdrawing anion include, but are not limited to, ammonium,trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H⁺,[H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron withdrawing components may be contacted with the oxide materialsimultaneously or individually, and any order that affords the desiredactivator-support acidity. For example, one aspect of this invention isemploying two or more electron-withdrawing anion source compounds in twoor more separate contacting steps. Thus, one example of such a processby which an activator-support is prepared is as follows: a selectedsolid oxide compound, or combination of oxide compounds, is contactedwith a first electron-withdrawing anion source compound to form a firstmixture, this first mixture is then calcined, the calcined first mixtureis then contacted with a second electron-withdrawing anion sourcecompound to form a second mixture, followed by calcining said secondmixture to form a treated solid oxide compound. In such a process, thefirst and second electron-withdrawing anion source compounds aretypically different compounds, although they may be the same compound.

In one aspect of the invention, the solid oxide activator-support isproduced by a process comprising:

1) contacting a solid oxide compound with at least oneelectron-withdrawing anion source compound to form a first mixture; and

2) calcining the first mixture to form the solid oxideactivator-support.

In another aspect of this invention, the solid oxide activator-supportis produced by a process comprising:

1) contacting at least one solid oxide compound with a firstelectron-withdrawing anion source compound to form a first mixture; and

2) calcining the first mixture to produce a calcined first mixture;

3) contacting the calcined first mixture with a secondelectron-withdrawing anion source compound to form a second mixture; and

4) calcining the second mixture to form the solid oxideactivator-support. Thus, the solid oxide activator-support is sometimesreferred to simply as a treated solid oxide or a chemically-treatedsolid oxide.

Another aspect of this invention producing or forming the solid oxideactivator-support by contacting at least one solid oxide with at leastone electron-withdrawing anion source compound, wherein the at least onesolid oxide compound is calcined before, during or after contacting theelectron-withdrawing anion source, and wherein there is a substantialabsence of aluminoxanes and organoboron compounds.

In one aspect of this invention, once the solid oxide has been treatedand dried, it may be subsequently calcined. Calcining of the treatedsolid oxide is generally conducted in an ambient atmosphere, typicallyin a dry ambient atmosphere, at a temperature from about 200° C. toabout 900° C., and for a time of about 1 minute to about 100 hours. Inanother aspect, calcining is conducted at a temperature from about 300°C. to about 800° C. and in another aspect, calcining is conducted at atemperature from about 400° C. to about 700° C. In yet another aspect,calcining is conducted from about 1 hour to about 50 hours, and inanother aspect calcining is conducted, from about 3 hours to about 20hours. In still another aspect, calcining may be carried out from about1 to about 10 hours at a temperature from about 350° C. to about 550° C.

Further, any type of suitable ambient can be used during calcining.Generally, calcining is conducted in an oxidizing atmosphere, such asair. Alternatively, an inert atmosphere, such as nitrogen or argon, or areducing atmosphere such as hydrogen or carbon monoxide, may be used.

In another aspect of the invention, the solid oxide component used toprepare the chemically-treated solid oxide has a pore volume greaterthan about 0.01 cc/g. In another aspect, the solid oxide component has apore volume greater than about 0.1 cc/g, and in yet another aspect,greater than about 1.0 cc/g. In still another aspect, the solid oxidecomponent has a surface area from about 1 to about 1000 m²/g. In anotheraspect, solid oxide component has a surface area from about 100 to about800 m²/g, and in still another aspect, from about 250 to about 600 m²/g.

The solid oxide material may be treated with a source of halide ion orsulfate ion, or a combination of anions, and optionally treated with ametal ion, then calcined to provide the activator-support in the form ofa particulate solid. In one aspect, the solid oxide material is treatedwith a source of sulfate, termed a sulfating agent, a source of chlorideion, termed a chloriding agent, a source of fluoride ion, termed afluoriding agent, or a combination thereof, and calcined to provide thesolid oxide activator. In another aspect, useful acidicactivator-supports include, but are not limited to: bromided alumina;chlorided alumina; fluorided alumina; sulfated alumina;bisulfate-treated alumina; bromided silica-alumina, chloridedsilica-alumina; fluorided silica-alumina; sulfated silica-alumina;bromided silica-zirconia, chlorided silica-zirconia; fluoridedsilica-zirconia; fluorided silica-titania; fluorided-chlorided alumina;sulfated silica-zirconia; chlorided zinc aluminate; chlorided tungstenaluminate; fluorided silica-boria; silica treated with fluoroborate; apillared clay such as a pillared montmorillonite, optionally treatedwith fluoride, chloride, or sulfate; phosphated alumina, or otheraluminophosphates, optionally treated with sulfate, fluoride, orchloride; or any combination thereof. Further, any of theactivator-supports may optionally be treated with a metal ion.

In one aspect of this invention, the treated oxide activator-supportcomprises a fluorided solid oxide in the form of a particulate solid,thus a source of fluoride ion is added to the oxide by treatment with afluoriding agent. In still another aspect, fluoride ion may be added tothe oxide by forming a slurry of the oxide in a suitable solvent such asalcohol or water, including, but are not limited to, the one to threecarbon alcohols because of their volatility and low surface tension.Examples of fluoriding agents that can be used in this inventioninclude, but are not limited to, hydrofluoric acid (HF), ammoniumfluoride (NH₄F), ammonium bifluoride (NH₄HF₂), ammoniumtetrafluoroborate (NH₄BF₄), ammonium silicofluoride (hexafluorosilicate)((NH₄)₂SiF₆), ammonium hexafluorophosphate (NH₄ PF₆), analogs thereof,and combinations thereof. For example, ammonium bifluoride NH₄HF₂ may beused as the fluoriding agent, due to its ease of use and readyavailability.

In another aspect of the present invention, the solid oxide can betreated with a fluoriding agent during the calcining step. Anyfluoriding agent capable of thoroughly contacting the solid oxide duringthe calcining step can be used. For example, in addition to thosefluoriding agents described previously, volatile organic fluoridingagents may be used. Examples of volatile organic fluoriding agentsuseful in this aspect of the invention include, but are not limited to,freons, perfluorohexane, perfluorobenzene, fluoromethane,trifluoroethanol, and combinations thereof. Gaseous hydrogen fluoride orfluorine itself can also be used with the solid oxide is fluoridedduring calcining. One convenient method of contacting the solid oxidewith the fluoriding agent is to vaporize a fluoriding agent into a gasstream used to fluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically-treatedsolid oxide comprises a chlorided solid oxide in the form of aparticulate solid, thus a source of chloride ion is added to the oxideby treatment with a chloriding agent. The chloride ion may be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Inanother aspect of the present invention, the solid oxide can be treatedwith a chloriding agent during the calcining step. Any chloriding agentcapable of serving as a source of chloride and thoroughly contacting theoxide during the calcining step can be used. For example, volatileorganic choriding agents may be used. Examples of volatile organicchoriding agents useful in this aspect of the invention include, but arenot limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, orany combination thereof. Gaseous hydrogen chloride or chlorine itselfcan also be used with the solid oxide during calcining. One convenientmethod of contacting the oxide with the chloriding agent is to vaporizea chloriding agent into a gas stream used to fluidize the solid oxideduring calcination.

In one aspect, the amount of fluoride or chloride ion present beforecalcining the solid oxide is generally from about 2 to about 50% byweight, where the weight percents are based on the weight of the solidoxide, for example silica-alumina, before calcining. In another aspect,the amount of fluoride or chloride ion present before calcining thesolid oxide is from about 3 to about 25% by weight, and in anotheraspect, from about 4 to about 20% by weight. If the fluoride or chlorideion are added during calcining, such as when calcined in the presence ofCCl₄, there is typically no fluoride or chloride ion in the solid oxidebefore calcining. Once impregnated with halide, the halided oxide may bedried by any method known in the art including, but not limited to,suction filtration followed by evaporation, drying under vacuum, spraydrying, and the like, although it is also possible to initiate thecalcining step immediately without drying the impregnated solid oxide.

The silica-alumina used to prepare the treated silica-alumina can have apore volume greater than about 0.5 cc/g. In one aspect, the pore volumemay be greater than about 0.8 cc/g, and in another aspect, the porevolume may be greater than about 1.0 cc/g. Further, the silica-aluminamay have a surface area greater than about 100 m²/g. In one aspect, thesurface area is greater than about 250 m²/g, and in another aspect, thesurface area may be greater than about 350 m²/g. Generally, thesilica-alumina of this invention has an alumina content from about 5 toabout 95%. In one aspect, the alumina content of the silica-alumina maybe from about 5 to about 50%, and in another aspect, the alumina contentof the silica-alumina may be from about 8% to about 30% alumina byweight.

The sulfated solid oxide comprises sulfate and a solid oxide componentsuch as alumina or silica-alumina, in the form of a particulate solid.Optionally, the sulfated oxide is further treated with a metal ion suchthat the calcined sulfated oxide comprises a metal. In one aspect, thesulfated solid oxide comprises sulfate and alumina. In one aspect ofthis invention, the sulfated alumina is formed by a process wherein thealumina is treated with a sulfate source, for example selected from, butnot limited to, sulfuric acid or a sulfate salt such as ammoniumsulfate. In one aspect, this process may be performed by forming aslurry of the alumina in a suitable solvent such as alcohol or water, inwhich the desired concentration of the sulfating agent has been added.Suitable organic solvents include, but are not limited to, the one tothree carbon alcohols because of their volatility and low surfacetension.

The amount of sulfate ion present before calcining is generally fromabout 1 to about 50% by weight, typically from about 5 to about 30% byweight, and more typically from about 10 to about 25% by weight, wherethe weight percents are based on the weight of the solid oxide beforecalcining. Once impregnated with sulfate, the sulfated oxide may bedried by any method known in the art including, but not limited to,suction filtration followed by evaporation, drying under vacuum, spraydrying, and the like, although it is also possible to initiate thecalcining step immediately.

In addition to being treated with an electron-withdrawing component suchas halide or sulfate ion, the solid inorganic oxide of this inventionmay optionally be treated with a metal source, including metal salts ormetal-containing compounds. In one aspect of the invention, thesecompounds may be added to or impregnated onto the solid oxide insolution form, and subsequently converted into the supported metal uponcalcining. Accordingly, the solid inorganic oxide can further comprise ametal selected from zinc, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, or a combination thereof. For example, zincmay be used to impregnate the solid oxide because it provides goodcatalyst activity and low cost. The solid oxide may be treated withmetal salts or metal-containing compounds before, after, or at the sametime that the solid oxide is treated with the electron-withdrawinganion.

Further, any method of impregnating the solid oxide material with ametal may be used. The method by which the oxide is contacted with ametal source, typically a salt or metal-containing compound, includes,but is not limited to, gelling, co-gelling, impregnation of one compoundonto another, and the like. Following any contacting method, thecontacted mixture of oxide compound, electron-withdrawing anion, and themetal ion is typically calcined. Alternatively, a solid oxide material,an electron-withdrawing anion source, and the metal salt ormetal-containing compound are contacted and calcined simultaneously.

In another aspect, the metallocene compound may be contacted with anolefin monomer and an organoaluminum cocatalyst for a first period oftime prior to contacting this mixture with the acidic activator-support.Once the precontacted mixture of metallocene, monomer, organoaluminumcocatalyst is contacted with the acidic activator-support, thecomposition further comprising the acidic activator-support is termedthe “postcontacted” mixture. The postcontacted mixture may be allowed toremain in further contact for a second period of time prior to beingcharged into the reactor in which the polymerization process will becarried out.

Various processes to prepare solid oxide activator-supports that can beemployed in this invention have been reported. For example, U.S. Pat.Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594,6,376,415, 6,391,816, 6,395,666, 6,524,987, and 6,548,441, describe suchmethods, each of which is incorporated by reference herein, in itsentirety.

The Optional Aluminoxane Cocatalyst

In one aspect, the present invention provides a catalyst compositioncomprising at least one metallocene, at least one organoaluminumcompound, at least one olefinic or acetylenic monomer, and at least oneacidic activator-support, and further comprising an optional cocatalyst.In one aspect, the optional cocatalyst may be selected from at least onealuminoxane, at least one organoboron compound, at least one ionizingionic compound, or any combination thereof. In another aspect, theoptional cocatalyst may be used in the precontacting step, in thepostcontacting step, or in both steps. Further, any combination ofcocatalysts may be used in either step, or in both steps.

Aluminoxanes are also referred to as poly(hydrocarbyl aluminum oxides)or simply organoaluminoxanes. The other catalyst components aretypically contacted with the aluminoxane in a saturated hydrocarboncompound solvent, though any solvent which is substantially inert to thereactants, intermediates, and products of the activation step can beused. The catalyst composition formed in this manner may be collected bymethods known to those of skill in the art, including but not limited tofiltration, or the catalyst composition may be introduced into thepolymerization reactor without being isolated.

The aluminoxane compound of this invention is an oligomeric aluminumcompound, wherein the aluminoxane compound can comprise linearstructures, cyclic, or cage structures, or typically mixtures of allthree. Cyclic aluminoxane compounds having the formula:

R is a linear or branched alkyl having from 1 to 10 carbon atoms, and nis an integer from 3 to about 10 are encompassed by this invention. The(AlRO)_(n) moiety shown here also constitutes the repeating unit in alinear aluminoxane. Thus, linear aluminoxanes having the formula:

R is a linear or branched alkyl having from 1 to 10 carbon atoms, and nis an integer from 1 to about 50, are also encompassed by thisinvention.

Further, aluminoxanes may also have cage structures of the formulaR_(5m+α) ^(t)R_(m−α) ^(b)Al_(4m)O_(3m), wherein m is 3 or 4 and α is=n_(Al(3))−n_(O(2))+n_(O(4)); wherein n_(Al(3)) is the number of threecoordinate aluminum atoms, n_(O(2)) is the number of two coordinateoxygen atoms, n_(O(4)) is the number of 4 coordinate oxygen atoms, R^(t)represents a terminal alkyl group, and R^(b) represents a bridging alkylgroup; wherein R is a linear or branched alkyl having from 1 to 10carbon atoms.

Thus, aluminoxanes that can serve as optional cocatalysts in thisinvention are generally represented by formulas such as (R—Al—O)_(n),R(R—Al—O)_(n)AlR₂, and the like, wherein the R group is typically alinear or branched C₁-C₆ alkyl such as methyl, ethyl, propyl, butyl,pentyl, or hexyl wherein n typically represents an integer from 1 toabout 50. In one embodiment, the aluminoxane compounds of this inventioninclude, but are not limited to, methylaluminoxane, ethylaluminoxane,n-propylaluminoxane, iso-propyl-aluminoxane, n-butylaluminoxane,t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentyl-aluminoxane,iso-pentylaluminoxane, neopentylaluminoxane, or combinations thereof.

While organoaluminoxanes with different types of R groups areencompassed by the present invention, methyl aluminoxane (MAO), ethylaluminoxane, or isobutyl aluminoxane are typical optional cocatalystsused in the catalyst compositions of this invention. These aluminoxanesare prepared from trimethylaluminum, triethylaluminum, ortriisobutylaluminum, respectively, and are sometimes referred to aspoly(methyl aluminum oxide), poly(ethyl aluminum oxide), andpoly(isobutyl aluminum oxide), respectively. It is also within the scopeof the invention to use an aluminoxane in combination with atrialkylaluminum, such as disclosed in U.S. Pat. No. 4,794,096, which isherein incorporated by reference in its entirety.

The present invention contemplates many values of n in the aluminoxaneformulas (R—Al—O)_(n) and R(R—Al—O)_(n)AlR₂, and preferably n is atleast about 3. However, depending upon how the organoaluminoxane isprepared, stored, and used, the value of n may be variable within asingle sample of aluminoxane, and such a combination oforganoaluminoxanes are comprised in the methods and compositions of thepresent invention.

In preparing the catalyst composition of this invention comprising anoptional aluminoxane, the molar ratio of the aluminum in the aluminoxaneto the metallocene in the composition is usually from about 1:10 toabout 100,000:1. In one another aspect, the molar ratio of the aluminumin the aluminoxane to the metallocene in the composition is usually fromabout 5:1 to about 15,000:1. The amount of optional aluminoxane added toa polymerization zone is an amount within a range of about 0.01 mg/L toabout 1000 mg/L, from about 0.1 mg/L to about 100 mg/L, or from about 1mg/L to abut 50 mg/L.

Organoaluminoxanes can be prepared by various procedures which are wellknown in the art. Examples of organoaluminoxane preparations aredisclosed in U.S. Pat. Nos. 3,242,099 and 4,808,561, each of which isincorporated by reference herein, in its entirety. One example of how analuminoxane may be prepared is as follows. Water which is dissolved inan inert organic solvent may be reacted with an aluminum alkyl compoundsuch as AlR₃ to form the desired organoaluminoxane compound. While notintending to be bound by this statement, it is believed that thissynthetic method can afford a mixture of both linear and cyclic(R—Al—O)_(n) aluminoxane species, both of which are encompassed by thisinvention. Alternatively, organoaluminoxanes may be prepared by reactingan aluminum alkyl compound such as AlR₃ with a hydrated salt, such ashydrated copper sulfate, in an inert organic solvent.

The Optional Organoboron Cocatalyst

In one aspect, the present invention provides a catalyst compositioncomprising at least one metallocene, at least one organoaluminumcompound, at least one olefinic or acetylenic monomer, and at least oneacidic activator-support, and further comprising an optional cocatalyst.In one aspect, the optional cocatalyst may be selected from at least onealuminoxane, at least one organoboron compound, at least one ionizingionic compound, or any combination thereof. In another aspect, theoptional cocatalyst may be used in the precontacting step, in thepostcontacting step, or in both steps. Further, any combination ofcocatalysts may be used in either step, or in both steps.

In one aspect, the organoboron compound comprises neutral boroncompounds, borate salts, or combinations thereof. For example, theorganoboron compounds of this invention can comprise a fluoroorganoboron compound, a fluoroorgano borate compound, or a combinationthereof. Any fluoroorgano boron or fluoroorgano borate compound known inthe art can be utilized. The term fluoroorgano boron compounds has itsusual meaning to refer to neutral compounds of the form BY₃. The termfluoroorgano borate compound also has its usual meaning to refer to themonoanionic salts of a fluoroorgano boron compound of the form[cation]⁺[BY₄]⁻, where Y represents a fluorinated organic group. Forconvenience, fluoroorgano boron and fluoroorgano borate compounds aretypically referred to collectively by organoboron compounds, or byeither name as the context requires.

Examples of fluoroorgano borate compounds that can be used ascocatalysts in the present invention include, but are not limited to,fluorinated aryl borates such as, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis-(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and the like, includingmixtures thereof. Examples of fluoroorgano boron compounds that can beused as cocatalysts in the present invention include, but are notlimited to, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, includingmixtures thereof.

Although not intending to be bound by the following theory, theseexamples of fluoroorgano borate and fluoroorgano boron compounds, andrelated compounds, are thought to form “weakly-coordinating” anions whencombined with organometal compounds, as disclosed in U.S. Pat. No.5,919,983, which is incorporated herein by reference in its entirety.

Generally, any amount of organoboron compound can be utilized in thisinvention. In one aspect, the molar ratio of the organoboron compound tothe metallocene compound in the composition is from about 0.1:1 to about10:1. Typically, the amount of the fluoroorgano boron or fluoroorganoborate compound used as a cocatalyst for the metallocene is in a rangeof from about 0.5 mole to about 10 moles of boron compound per mole ofmetallocene compound. In one aspect, the amount of fluoroorgano boron orfluoroorgano borate compound used as a cocatalyst for the metallocene isin a range of from about 0.8 mole to about 5 moles of boron compound permole of metallocene compound.

The Optional Ionizing Ionic Compound Cocatalyst

In one aspect, the present invention provides a catalyst compositioncomprising at least one metallocene, at least one organoaluminumcompound, at least one olefinic or acetylenic monomer, and at least oneacidic activator-support, and further comprising an optional cocatalyst.In one aspect, the optional cocatalyst may be selected from at least onealuminoxane, at least one organoboron compound, at least one ionizingionic compound, or any combination thereof. In another aspect, theoptional cocatalyst may be used in the precontacting step, in thepostcontacting step, or in both steps. Further, any combination ofcocatalysts may be used in either step, or in both steps. Examples ofionizing ionic compound are disclosed in U.S. Pat. Nos. 5,576,259 and5,807,938, each of which is incorporated herein by reference, in itsentirety.

An ionizing ionic compound is an ionic compound which can function toenhance activity of the catalyst composition. While not bound by theory,it is believed that the ionizing ionic compound may be capable ofreacting with the metallocene compound and converting the metalloceneinto a cationic metallocene compound. Again, while not intending to bebound by theory, it is believed that the ionizing ionic compound mayfunction as an ionizing compound by completely or partially extractingan anionic ligand, possibly a non-η⁵-alkadienyl ligand such as (X³) or(X⁴), from the metallocene. However, the ionizing ionic compound is anactivator regardless of whether it is ionizes the metallocene, abstractsan (X³) or (X⁴) ligand in a fashion as to form an ion pair, weakens themetal-(X³) or metal-(X⁴) bond in the metallocene, simply coordinates toan (X³) or (X⁴) ligand, or any other mechanisms by which activation mayoccur. Further, it is not necessary that the ionizing ionic compoundactivate the metallocene only. The activation function of the ionizingionic compound is evident in the enhanced activity of catalystcomposition as a whole, as compared to a catalyst composition containingcatalyst composition that does not comprise any ionizing ionic compound.

Examples of ionizing ionic compounds include, but are not limited to,the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate,tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammoniumtetrakis(2,4-dimethyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate,N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbeniumtetrakis(m-tolyl)borate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)borate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate,tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate,lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate,lithium tetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl) borate,sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate,tri(n-butyl)ammonium tetrakis(p-tolyl)aluminate, tri(n-butyl)ammoniumtetrakis(m-tolyl)aluminate, tri(n-butyl)ammoniumtetrakis(2,4-dimethyl)aluminate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl) aluminate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)aluminate, N,N-dimethylaniliniumtetrakis(p-tolyl)aluminate, N,N-dimethylaniliniumtetrakis(m-tolyl)aluminate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)aluminate, N,N-dimethylaniliniumtetrakis(3,5-dimethyl-phenyl)aluminate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)aluminate, triphenylcarbeniumtetrakis(p-tolyl)aluminate, triphenylcarbeniumtetrakis(m-tolyl)aluminate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis-(pentafluorophenyl)aluminate, tropyliumtetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate,tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropyliumtetrakis(3,5-dimethylphenyl)aluminate, tropyliumtetrakis(pentafluorophenyl)aluminate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetrakis(phenyl)aluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetrakis(phenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetrakis(phenyl)aluminate, potassium tetrakis(p-tolyl)aluminate,potassium tetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, However,the ionizing ionic compound is not limited thereto in the presentinvention.

Preparation of the Catalyst Composition

In accordance with this invention, the catalyst compositions may beprepared by a process comprising precontacting an organoaluminumcocatalyst compound with an olefin or alkyne and an organometal compoundfor an effective period of time, before this mixture is contacted withthe activator-support for an effective period of time. In one aspect,the process of preparing the catalyst of this invention may occur in aninert atmosphere and under substantially anhydrous conditions. Thus, theatmosphere is substantially oxygen-free and substantially free of wateras the reaction begins, to prevent deactivation of the catalyst. In oneaspect of this invention, for example, 1-hexene, triethylaluminum, and azirconium metallocene, such as bis(indenyl)zirconium dichloride orbis(cyclopentadienyl)zirconium dichloride are precontacted for at leastabout 30 minutes prior to contacting this mixture with a fluoridedsilica-alumina activator-support. Once this precontacted mixture isbrought into contact with the activator-support, this postcontactedmixture is allowed to remain in contact for from about 1 minute to about24 hours, typically from about 5 minutes to about 5 hours, and moretypically from about 10 minutes to about 1 hour, prior to using thismixture in a polymerization process.

Typically, the mixture of metallocene, olefin or alkyne monomer, andorganoaluminum compound, before it is contacted with theactivator-support, is termed the “precontacted” mixture. Accordingly,the components of the precontacted mixture are termed precontactedmetallocene, precontacted olefin or alkyne monomer, and precontactedorganoaluminum compound. The mixture of the precontacted mixture and theacidic activator-support, that is, the mixture of the metallocene,olefin or alkyne monomer, organoaluminum compound, and acidicactivator-support, is typically termed the “postcontacted” mixture.Accordingly, the components of the postcontacted mixture are termedpostcontacted metallocene, postcontacted olefin or alkyne monomer,postcontacted organoaluminum compound, and postcontacted acidicactivator-support.

In one aspect of this invention, improved catalytic activities may beachieved when the precontacted mixture comprises various componentsother than the metallocene, olefin or alkyne monomer, and organoaluminumcompound. In this aspect, the components of the precontacted mixture andthe postcontacted mixture vary, such that the resulting catalystcomposition can be tailored for the desired activity, or to accommodatea particular polymerization process.

The precontacting step may be carried out in a variety of ways,including but not limited to, blending. Furthermore, each of theorganometal, monomer, and organoaluminum cocatalyst compounds can be fedinto a reactor separately, or various combinations of these compoundscan be contacted with each other before being further contacted in thereactor. Alternatively, all three compounds can be contacted togetherbefore being introduced into the reactor. Typically, the mixture ofmetallocene, alkene or alkyne, and organoaluminum compound wasprecontacted from minutes to days in a separate reactor, prior tocontacting this mixture with activator-support to form the postcontactedmixture. This precontacting step is usually carried out under an inertatmosphere. Further, the precontacting step may be carried out withstirring, agitation, heating, cooling, sonication, shaking, underpressure, at room temperature, in an inert solvent (typically ahydrocarbon), and the like. However, such conditions are not necessaryas the precontacting step may be carried out by simply allowing thecomponents to stand substantially undisturbed.

In another aspect of this invention, the precontacted mixture isprepared first by contacting an organoaluminum compound, an olefin oracetylene, and an organometal (typically a metallocene) compound beforeinjection into the reactor, typically for about 1 minute to about 9days, more typically from about 1 minute to about 24 hours. Thecomponents of the precontacted mixture are generally contacted at atemperature from about 10° C. to about 200° C., typically from about 15°C. to about 80° C. This precontacted mixture is then placed in contactwith the acidic activator-support, typically a fluorided silica-aluminaactivator-support as disclosed herein, to form the postcontactedmixture.

The postcontacted mixture is prepared by contacting and admixing theacidic activator-support and the precontacted mixture for any length oftime and at any temperature and pressure that allows complete contactand reaction between the components of the postcontacted mixture. Forexample, this postcontacted mixture is usually allowed to remain incontact for from about 1 minute to about 24 hours, typically from about5 minutes to about 5 hours, and more typically from about 10 minutes toabout 1 hour, prior to using this mixture in a polymerization process.Once the acidic activator-support and the precontacted mixture have beenin contact for a period of time, the composition comprises apost-contacted organometal compound (typically, a metallocene), apostcontacted organoaluminum compound, a postcontacted olefin or alkyne,and a postcontacted acidic activator-support (typically fluoridedsilica-alumina). Generally, the postcontacted acidic activator-supportis the majority, by weight, of the composition. Often, the specificnature of the final components of a catalyst prepared as describedherein are not known, therefore the catalyst composition of the presentinvention is described as comprising postcontacted compounds andcomponents. Further, because the exact order of contacting can bevaried, it is believed that this terminology is best to describe thecomposition's components.

In one aspect, the postcontacting step in which the precontacted mixtureis placed in contact with the acidic activator-support is typicallycarried out in an inert atmosphere. Contact times between the acidicactivator-support and the precontacted mixture typically range from timeabout 0.1 hour to about 24 hours, and from 0.1 to about 1 hours is moretypical. The mixture may be heated to a temperature from between about0° F. to about 150° F. Temperatures between about 40° F. to about 95° F.are typical if the mixture is heated at all. While not intending to bebound by theory, these conditions are thought to assist in thedeposition of a catalytically-effective amount of the catalyst on theacidic activator-support.

In general, heating is carried out at a temperature and for a durationsufficient to allow adsorption, impregnation, or interaction ofprecontacted mixture and the acidic activator-support, such that aportion of the components of the precontacted mixture is immobilized,adsorbed, or deposited thereon. For example, in one aspect, a catalystcomposition of this invention is prepared by contacting 1-hexene,triethylaluminum, and a zirconium metallocene, such asbis(indenyl)zirconium dichloride or bis(cyclopentadienyl)zirconiumdichloride for at least about 30 minutes, followed by contacting thisprecontacted mixture with a fluorided silica-alumina activator-supportfor at least about 10 minutes up to one hour to form the activecatalyst.

More than one metallocene can be used in the catalyst composition andmethods of the present invention. When a catalyst composition comprisesmore than one metallocene, the metallocene compounds are employed in oneor more precontacted mixtures. Thus, these multiple metallocenes may beemployed in the same precontacted mixture and then used in the samepostcontacted mixture, they can be employed in different precontactedmixtures which are then used to prepare the same postcontacted mixture,or they can be employed in different precontacted mixtures and differentpostcontacted mixtures which are then introduced into the polymerizationreactor.

In one aspect, the molar ratio of the organometal or metallocenecompound to the organoaluminum compound is about 1:1 to about 1:10,000,typically from about 1:1 to about 1:1,000, and more typically from about1:1 to about 1:100. These molar ratios reflect the ratio of metallocenecompound to the total amount of organoaluminum compound in both theprecontacted mixture and the postcontacted mixture.

Generally, the molar ratio of olefin or alkyne monomer to organometal ormetallocene compound in the precontacted mixture is about 1:10 to about100,000:1, typically from about 10:1 to about 1,000:1.

In another aspect of this invention, the weight ratio of the acidicactivator-support to the organoaluminum compound generally ranges fromabout 1:5 to about 1,000:1, typically from about 1:3 to about 100:1, andmore typically from about 1:1 to about 50:1. In a further aspect of thisinvention, the weight ratio of the metallocene to the acidicactivator-support is typically from about 1:1 to about 1:10,000,000,more typically from about 1:10 to about 1:100,000, even more typicallyfrom about 1:20 to about 1:1000. These ratios that involve the acidicactivator-support are based on the amount of the components that havebeen added to make up the postcontacted mixture to provide the catalystcomposition.

One aspect of this invention is that aluminoxane is not required to formthe catalyst composition disclosed herein, a feature that allows lowerpolymer production costs. Accordingly, the present invention uses onlyAlR₃-type organoaluminum compounds which does not activate themetallocene catalyst in the same manner as an organoaluminoxane.Additionally, no expensive borate compounds or MgCl₂ are required toform the catalyst composition of this invention, although aluminoxane,borate compounds, MgCl₂, or combinations thereof can optionally be usedin some aspects of this invention. However, another aspect of thisinvention is the use of optional cocatalysts, including, but not limitedto, at least one aluminoxane, at least one organoboron compound, atleast one ionizing ionic compound, or any combination thereof.

It is believed that the unexpected enhancements in the catalyticactivity observed from precontacting certain catalyst components may berelated to the formation of organoaluminum metallacyclic compounds,based upon the reported synthesis of aluminacyclopentanes (ACPs)according to the following reaction scheme, Scheme 1, using(η⁵-C₅H₅)₂ZrCl₂, AlEt₃, and CH₂═CHCH₂R (R═C₃H₇, C₅H₁₁, or C₈H₁₇), whereη⁵-C₅H₅═Cp.

One reaction scheme to produce ACPs is described in: U. M. Dzhemilev andA. G. Ibragimov, Journal of Organometallic Chemistry, 1994, 466, 1-4,which, along with the references and citations referred to therein, eachof which is incorporated by reference herein, in its entirety. Otherreaction schemes to produce ACPs are described in Khalikov, L. M.;Parfenova, L. V.; Rusakov, S. V.; Ibragimov, A. G.; Dzhemilev, U. M.Russian Chemical Bulletin, International Addition 2000, 49, (12),2051-2058. See also: Negishi, E.; Kondakov, Denis, Y.; Choueiry, D.;Kasai, K.; Takahashi, T. Journal of the American Chemical Society 1996,118, 9577-9588, each of which is incorporated by referenced herein, inits entirety. According to Scheme 1, when the organometal (typicallymetallocene) compound and an organoaluminum compound are precontactedwith an olefin, an aluminacyclopentane can form. While not intending tobe bound by this statement, according to this reaction scheme andanalogous reactions schemes described in Dzhemilev, U. M.; Ibragimov, A.G. Russian Chemical Reviews 2000, 69, (2) 121-135 when the organometal(typically metallocene) compound and an organoaluminum compound areprecontacted with an alkyne, an aluminacyclopentene can form. A mixtureof an olefin and an alkyne in the precontacted mixture would be expectedto form an aluminacyclopentane and an aluminacyclopentene, in ananalogous manner.

In accordance with Khalikov, L. M.; Parfenova, L. V.; Rusakov, S. V.;Ibragimov, A. G.; Dzhemilev, U. M. Russian Chemical Bulletin,International Addition 2000, 49, (12), 2051-2058, and the references andcitations referred to therein, there are several possible mechanisms bywhich Scheme 1 can operate, one of which is presented in Scheme 2. Notethat only one regioisomer of intermediate B is shown, leading to thealuminacyclopentane (ACP) regioisomer C shown.

However, this scheme would also be expected to provide some of theα-substituted aluminacyclopentane, structure D, shown here:

Thus, for any particular compound disclosed herein, any generalstructure presented also encompasses all isomers, including allregioisomers, that may arise from a particular set of substituents orfrom a particular reaction scheme, as the context requires.

Another aspect of this invention is the catalyst composition comprisingaluminacyclopentanes or metallacyclopentane of a metallocene, such as azirconacyclopentanes. Thus, this invention encompasses a catalystcomposition comprising a precontacted metallocene, a precontacted olefinor alkyne, a postcontacted acidic activator-support, and analuminacyclopentane. This invention also encompasses a catalystcomposition comprising a precontacted metallocene, a precontacted olefinor alkyne, a postcontacted acidic activator-support, and ametallacyclopentane or a metallacyclopentene of a metallocene.

Also, while not intending to be bound by theoretical statements, thereaction schemes above may also explain why triethylaluminum (TEA) workswell to form the precontacted solution, while trimethylaluminum (TMA)does not. As indicated in Scheme 2, if the aluminum alkyl compound usedin the precontacted mixture contains β-hydrogen atoms, these alkylgroups can participate in the β-H elimination process shown whencoordinated to the organometal compound, thereby forming thezirconium-aluminum compound and the resulting zirconacyclopentane andACP. The ethyl groups of TEA have β-hydrogen atoms while the methylgroups of TMA do not.

While not intending to be bound by the theory, it is believed thatdifferent aluminacyclopentanes (ACPs) can arise when two olefins arepresent in solution. For example, if both CH₂═CHCH₂R and CH₂═CH₂ arepresent in solution, additional aluminacyclopentanes analogous to C andD are believed to be accessible in a precontact solution that containedboth CH₂═CHCH₂R and CH₂═CH₂ (regardless of whether the ethylene wasintroduced or was derived from AlEt₃), which could also give rise to thefollowing aluminacyclopentanes E-H, derived from homocoupling of thesame two olefins at a single metal site:

As illustrated in Scheme 2, these various aluminacyclopentanes wouldarise from the analogous zirconacyclopentanes.

In another aspect, this invention encompasses a catalyst compositionthat comprises a precontacted metallocene, a precontacted olefin oralkyne, a postcontacted acidic activator-support, and analuminacyclopentane. Thus, the catalyst composition of this inventioncan comprise an aluminacyclopentane (E, F, G, H), an aluminacyclopentene(I), or an aluminacyclopentadiene (e.g., see Negishi, E.; Kondakov,Denis, Y.; Choueiry, D.; Kasai, K.; Takahashi, T. Journal of theAmerican Chemical Society 1996, 118, 9577-9588, Scheme 17, cited above),whether generated by the reaction schemes disclosed herein, or whetherprepared independently. Similarly, this invention also encompasses acatalyst composition that comprises a precontacted metallocene, aprecontacted olefin or alkyne, a postcontacted acidic activator-support,and a zirconacyclic species. As indicated in Scheme 2 and the referencescited above, this cyclic organometal species can be azirconacyclopentane (J) or a zirconacyclopentene (K) of any metalloceneused in this invention, whether generated by the reaction schemesdisclosed above,

or whether prepared independently.

The formation of an aluminacyclopentane upon precontacting a metallocenecompound, an organoaluminum compound, and an olefin in the presentinvention was monitored by gas chromatography of the hydrolysis productsof the aluminacyclopentane, as well as by gas (ethane) evolution whenTEA is employed as the an organoaluminum compound. Accordingly, oneaspect of this invention comprises preparing organoaluminummetallacyclic compounds, based upon the synthesis ofaluminacyclopentanes reported in U. M. Dzhemilev and A. G. Ibragimov,Journal of Organometallic Chemistry, 1994, 466, 1-4, and using thereaction mixture comprising the aluminacyclopentanes in place of theprecontacted mixture, according to the present reaction.

In another aspect of this invention, the components of the precontactedmixture and the postcontacted mixture vary, such that the resultingcatalyst composition can be tailored for the desired activity, or themethod of preparing the catalyst composition can accommodate the desiredpolymerization process. For example, in one aspect, the catalystcomposition of this invention comprises a precontacted metallocene, aprecontacted organoaluminum compound, a postcontacted olefin or alkyne,and a postcontacted acidic activator-support. In another aspect, thecatalyst composition of this invention comprises a precontactedmetallocene, a postcontacted organoaluminum compound, a precontactedolefin or alkyne, and a postcontacted acidic activator-support. In afurther aspect, the catalyst composition of this invention comprises aprecontacted metallocene, a postcontacted organoaluminum compound, aprecontacted olefin or alkyne, and a precontacted acidicactivator-support. In yet another aspect, the catalyst composition ofthis invention comprises a precontacted metallocene, a precontactedolefin or alkyne, a postcontacted acidic activator-support, and analuminacyclopentane or aluminacyclopentene. In each of these aspects inwhich the components of the precontacted or postcontacted mixtures vary,the relative amounts of each component in the precontacted orpostcontacted mixtures are typically within the same ranges as thosedisclosed here for the catalyst composition comprising a precontactedmetallocene, a precontacted organoaluminum compound, a precontactedolefin or alkyne, and a postcontacted acidic activator-support.

Utility of the Catalyst Composition in Polymerization Processes

In one aspect, catalyst composition of this invention can have anactivity greater than a catalyst composition that uses the samecomponents, but does not involve precontacting the organometal compound,the organoaluminum compound, and an olefin or alkyne monomer.

Polymerizations using the catalysts of this invention can be carried outin any manner known in the art. Such polymerization processes include,but are not limited to slurry polymerizations, gas phasepolymerizations, solution polymerizations, and the like, includingmulti-reactor combinations thereof. Thus, any polymerization zone knownin the art to produce ethylene-containing polymers can be utilized. Forexample, a stirred reactor can be utilized for a batch process, or thereaction can be carried out continuously in a loop reactor or in acontinuous stirred reactor.

After catalyst activation, a catalyst composition is used tohomopolymerize ethylene, or copolymerize ethylene with a comonomer. Inone aspect, a typical polymerization method is a slurry polymerizationprocess (also known as the particle form process), which is well knownin the art and is disclosed, for example in U.S. Pat. No. 3,248,179,which is incorporated by reference herein, in its entirety. Otherpolymerization methods of the present invention for slurry processes arethose employing a loop reactor of the type disclosed in U.S. Pat. No.3,248,179, and those utilized in a plurality of stirred reactors eitherin series, parallel, or combinations thereof, wherein the reactionconditions are different in the different reactors, which is alsoincorporated by reference herein, in its entirety.

In one aspect, polymerization temperature for this invention may rangefrom about 60° C. to about 280° C., and in another aspect,polymerization reaction temperature may range from about 70° C. to about110° C.

In another aspect, the polymerization reaction typically occurs in aninert atmosphere, that is, in atmosphere substantial free of oxygen andunder substantially anhydrous conditions, thus, in the absence of wateras the reaction begins. Therefore a dry, inert atmosphere, for example,dry nitrogen or dry argon, is typically employed in the polymerizationreactor.

In still another aspect, the pretreatment pressure can be any pressurethat does not terminate the pretreatment step, and typically is selectedfrom a pressure that is suitable for the formation of organoaluminummetallacyclic compounds such as aluminacyclopentanes (ACPs), uponprecontacting the metallocene, organoaluminum compound, and an olefin.Pretreatment pressures are typically, but not necessarily, lower thanpolymerization pressures, and generally range from about atmosphericpressure to about 100 psig. In one aspect, pretreatment pressures arefrom about atmospheric pressure to about 50 psig.

In yet another aspect, the polymerization reaction pressure can be anypressure that does not terminate the polymerization reaction, and ittypically conducted at a pressure higher than the pretreatmentpressures. In one aspect, polymerization pressures may be from aboutatmospheric pressure to about 1000 psig. In another aspect,polymerization pressures may be from about 50 psig to about 800 psig.Further, hydrogen can be used in the polymerization process of thisinvention to control polymer molecular weight.

When a copolymer of ethylene is prepared according to this invention,comonomer is introduced into the reaction zone in sufficient quantity toproduce the desired polymer composition. A typical copolymer compositionis generally from about 0.01 to about 10 weight percent comonomer basedon the total weight of the monomer and comonomer, however this copolymercomposition varies outside this range depending upon the copolymerspecification and desired composition. Thus, any amount of copolymersufficient to give the described polymer composition in the copolymerproduced can be used.

Polymerizations using the catalysts of this invention can be carried outin any manner known in the art. Such processes that can polymerizemonomers into polymers include, but are not limited to slurrypolymerizations, gas phase polymerizations, solution polymerizations,and multi-reactor combinations thereof. Thus, any polymerization zoneknown in the art to produce olefin-containing polymers can be utilized.In one aspect, for example, a stirred reactor can be utilized for abatch process, or the reaction can be carried out continuously in a loopreactor or in a continuous stirred reactor. In another aspect, forexample, the polymerizations disclosed herein are carried out using aslurry polymerization process in a loop reaction zone. Suitable diluentsused in slurry polymerization are well known in the art and includehydrocarbons which are liquid under reaction conditions. The term“diluent” as used in this disclosure does not necessarily mean an inertmaterial, as this term is meant to include compounds and compositionsthat may contribute to polymerization process. Examples of hydrocarbonsthat can be used as diluents include, but are not limited to,cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane,neopentane, and n-hexane. Typically, isobutane is used as the diluent ina slurry polymerization. Examples of this technology are found in U.S.Pat. Nos. 4,424,341; 4,501,885; 4,613,484; 4,737,280; and 5,597,892;each of which is incorporated by reference herein, in its entirety.

For purposes of the invention, the term polymerization reactor includesany polymerization reactor or polymerization reactor system known in theart that is capable of polymerizing olefin monomers to producehomopolymers or copolymers of the present invention. Such reactors cancomprise slurry reactors, gas-phase reactors, solution reactors, or anycombination thereof. Gas phase reactors can comprise fluidized bedreactors or tubular reactors. Slurry reactors can comprise verticalloops or horizontal loops. Solution reactors can comprise stirred tankor autoclave reactors.

Polymerization reactors suitable for the present invention can compriseat least one raw material feed system, at least one feed system forcatalyst or catalyst components, at least one reactor system, at leastone polymer recovery system or any suitable combination thereof.Suitable reactors for the present invention can further comprise anyone, or combination of, a catalyst storage system, an extrusion system,a cooling system, a diluent recycling system, or a control system. Suchreactors can comprise continuous take-off and direct recycling ofcatalyst, diluent, and polymer. Generally, continuous processes cancomprise the continuous introduction of a monomer, a catalyst, and adiluent into a polymerization reactor and the continuous removal fromthis reactor of a suspension comprising polymer particles and thediluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor per system or multiple reactor systems comprising two ormore types of reactors operated in parallel or in series. Multiplereactor systems can comprise reactors connected together to performpolymerization, or reactors that are not connected. The polymer can bepolymerized in one reactor under one set of conditions, and then thepolymer can be transferred to a second reactor for polymerization undera different set of conditions.

In one aspect of the invention, the polymerization reactor system cancomprise at least one loop slurry reactor. Such reactors are known inthe art and can comprise vertical or horizontal loops. Such loops cancomprise a single loop or a series of loops. Multiple loop reactors cancomprise both vertical and horizontal loops. The slurry polymerizationcan be performed in an organic solvent that can disperse the catalystand polymer. Examples of suitable solvents include butane, hexane,cyclohexane, octane, and isobutane. Monomer, solvent, catalyst and anycomonomer are continuously fed to a loop reactor where polymerizationoccurs. Polymerization can occur at low temperatures and pressures.Reactor effluent can be flashed to remove the solid resin.

In yet another aspect of this invention, the polymerization reactor cancomprise at least one gas phase reactor. Such systems can employ acontinuous recycle stream containing one or more monomers continuouslycycled through the fluidized bed in the presence of the catalyst underpolymerization conditions. The recycle stream can be withdrawn from thefluidized bed and recycled back into the reactor. Simultaneously,polymer product can be withdrawn from the reactor and new or freshmonomer can be added to replace the polymerized monomer. Such gas phasereactors can comprise a process for multi-step gas-phase polymerizationof olefins, in which olefins are polymerized in the gaseous phase in atleast two independent gas-phase polymerization zones while feeding acatalyst-containing polymer formed in a first polymerization zone to asecond polymerization zone.

In still another aspect of the invention, the polymerization reactor cancomprise a tubular reactor. Tubular reactors can make polymers by freeradical initiation, or by employing the catalysts typically used forcoordination polymerization. Tubular reactors can have several zoneswhere fresh monomer, initiators, or catalysts are added. Monomer can beentrained in an inert gaseous stream and introduced at one zone of thereactor. Initiators, catalysts, and/or catalyst components can beentrained in a gaseous stream and introduced at another zone of thereactor. The gas streams are intermixed for polymerization. Heat andpressure can be employed appropriately to obtain optimal polymerizationreaction conditions.

In another aspect of the invention, the polymerization reactor cancomprise a solution polymerization reactor. During solutionpolymerization, the monomer is contacted with the catalyst compositionby suitable stirring or other means. A carrier comprising an inertorganic diluent or excess monomer can be employed. If desired, themonomer can be brought in the vapor phase into contact with thecatalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed during polymerization toobtain better temperature control and to maintain uniform polymerizationmixtures throughout the polymerization zone. Adequate means are utilizedfor dissipating the exothermic heat of polymerization. Thepolymerization can be effected in a batch manner, or in a continuousmanner. The reactor can comprise a series of at least one separator thatemploys high pressure and low pressure to separate the desired polymer.

In a further aspect of the invention, the polymerization reactor systemcan comprise the combination of two or more reactors. Production ofpolymers in multiple reactors can include several stages in at least twoseparate polymerization reactors interconnected by a transfer devicemaking it possible to transfer the polymers resulting from the firstpolymerization reactor into the second reactor. The desiredpolymerization conditions in one of the reactors can be different fromthe operating conditions of the other reactors. Alternatively,polymerization in multiple reactors can include the manual transfer ofpolymer from one reactor to subsequent reactors for continuedpolymerization. Such reactors can include any combination including, butnot limited to, multiple loop reactors, multiple gas reactors, acombination of loop and gas reactors, a combination of autoclavereactors or solution reactors with gas or loop reactors, multiplesolution reactors, or multiple autoclave reactors.

In another aspect of this invention, the catalyst can be made in avariety of methods, including, but not limited to, continuously feedingthe catalyst components directly into the polymerization reactor,including at least one optional precontacting step of some or all thecatalyst components prior to introducing them into the reactor. In thisaspect, each optional precontacting steps can involve precontacting fora different time period. In this aspect, the invention can encompassmultiple, optional precontacting steps, for multiple time periods, priorto initiating the polymerization reaction. Further, these multiple,optional precontacting steps can take place in at least oneprecontacting vessel prior to introducing the precontacted componentsinto the reactor, they can take place in the polymerization reactoritself, or any combination thereof, including the use of multipleprecontacting vessels comprising different catalyst components. Thus, inthis aspect, any precontacting steps can encompass precontacting of anycombination of catalyst components, including any optional catalystcomponents. Also in this aspect, the multiple, optional precontactingsteps can involve different precontacting time periods.

In another aspect of this invention, the catalyst can be made bycontinuously feeding the catalyst components into any number of optionalprecontacting vessels and subsequently introducing the componentscontinuously into the reactor. In one aspect, for example, the presentinvention provides a process to produce a catalyst composition,comprising:

-   -   contacting at least one metallocene, at least one organoaluminum        compound, and at least one olefin or alkyne for a first period        of time to form a precontacted mixture comprising at least one        precontacted metallocene, at least one precontacted        organoaluminum compound, and at least one precontacted olefin or        alkyne; and    -   contacting the precontacted mixture with at least one acidic        activator-support for a second period of time to form a        postcontacted mixture comprising at least one postcontacted        metallocene, at least one postcontacted organoaluminum compound,        at least one postcontacted olefin or alkyne, and at least one        postcontacted acidic activator-support.

In another aspect, for example, the present invention provides a processto produce a catalyst composition, comprising:

-   -   contacting at least two catalyst components selected from at        least one metallocene, at least one organoaluminum compound, at        least one olefin or alkyne, or at least one acidic        activator-support for a first period of time to form a        precontacted mixture comprising precontacted catalyst        components; and    -   contacting the precontacted mixture with any catalyst components        not used to form the precontacted mixture, and optionally        contacting the precontacted mixture with additional catalyst        components selected from at least one metallocene, at least one        organoaluminum compound, at least one olefin or alkyne, or at        least one acidic activator-support for a second period of time        to form a postcontacted mixture comprising at least one        postcontacted metallocene, at least one postcontacted        organoaluminum compound, at least one postcontacted olefin or        alkyne, and at least one postcontacted acidic activator-support.

In another aspect, each ingredient can be fed to the reactor, eitherdirectly or through at least one precontacting vessel, using knownfeeding, measuring, and controlling devices, such as pumps, mass andvolumetric flow meters and controllers, and the like. Feed-back signalsand control loops can be used in connection with this continuouscatalyst formation and introduction. The mass flow meter can be acoriolis-type meter adapted to measure a variety of flow types such asfrom a positive displacement-type pump with three heads. Other types ofpumps, meters, and combinations of similar types of devices can be usedas means for feed and control to measure and control a feed rate of acatalyst component. Various combinations of means for feed and controlcan also be used for each respective component depending upon the typeof component, chemical compatibility of the component, and the desiredquantity and flow rate of the component, and as well known to one ofordinary skill in the art. For example, a suitable meter for means forfeed and control can be, but is not limited to, a thermal mass flowmeter, a volumetric flow meter such as an orifice-type, diaphragm-type,a level-type meter, or the like.

In another aspect, the catalyst components can be combined in a varietyor different orders and combinations prior to being introduced into thepolymerization reactor. In one aspect, for example, the metallocene canbe precontacted with an aluminum alkyl and an olefin in a firstprecontacting vessel, for a first precontacting time, for example, up to7-10 days, to form a first precontacted solution. This firstprecontacted solution can then be fed to a second precontacting vesselalong with the treated solid oxide component, and optionally morealuminum alkyl, for a second precontacting time. In this aspect, forexample, the second precontacting time can be shorter, longer, or thesame as the first precontacting time. For example, the secondprecontacting time can be about 0.5 hour, after which the“postcontacted” mixture can be fed from the second precontacting vesseldirectly into the reactor itself. In another aspect of this invention,all of the catalyst components can be brought together in theprecontacting vessel for the first period of time, prior to beingintroduced directly into the reactor.

In another aspect, a portion of each catalyst component can be fed intothe reactor directly, while the remainder is fed into a precontactingvessel. In this aspect, for example, it is sometimes desirable to limitthe exposure of the metallocene or treated solid oxide to the aluminumalkyl, in which case only a small amount of aluminum alkyl can beintroduced into the precontacting vessel, either alone or from asolution also containing the olefin and metallocene, while the remainderof the aluminum alkyl can be fed directly into the reactor. Likewise,the amount of olefin fed as part of the catalyst preparation may be fedfrom multiple sources. For example, 1-hexene may be added to themetallocene solution in a first precontacting step to form a firstprecontacted solution, more 1-hexene may be added separately in a secondprecontacting step to form a second precontacted solution, and stillmorel-hexene may be added directly to the reactor. Similarly any of theother catalyst components can also be added in multiple steps to theentire reactor system.

After the polymers are produced, they can be formed into variousarticles, including but not limited to, household containers, utensils,film products, drums, fuel tanks, pipes, geomembranes, and liners.Various processes can form these articles. In one aspect, additives andmodifiers can be added to the polymer in order to provide particulardesired effects.

DEFINITIONS

In order to more clearly define the terms used herein, the followingdefinitions are provided. To the extent that any definition or usageprovided by any document incorporated herein by reference conflicts withthe definition or usage provided herein, the definition or usageprovided herein controls.

The term polymer is used herein to mean homopolymers comprisingethylene, copolymers of ethylene and another olefinic comonomer, or anycombination thereof. The term polymer is also used herein to meanhomopolymers and copolymers of acetylenes.

The term cocatalyst is used herein to refer to the at least oneorganoaluminum compound that constitutes a component of the catalystmixture. Typical cocatalysts are trialkyl aluminum compounds, dialkylaluminum halide compounds, and alkyl aluminum dihalide compounds. Theterm cocatalyst may be used regardless of the actual function of thecompound or any chemical mechanism by which the compound may operate.

The term inert atmosphere is used herein to refer to any type of ambientatmosphere that is substantially unreactive toward the particularreaction, process, or material around which the atmosphere surrounds orblankets. Thus, this term is typically used herein to refer to the useof a substantially oxygen-free and moisture-free blanketing gas,including but not limited to dry argon, dry nitrogen, dry helium, ormixtures thereof, when any precursor, component, intermediate, orproduct of a reaction or process is sensitive to particular gases ormoisture. Additionally, inert atmosphere is also used herein to refer tothe use of dry air as a blanketing atmosphere when the precursors,components, intermediates, or products of the reaction or process areonly moisture-sensitive and not oxygen-sensitive. However, inertatmosphere as used herein would typically exclude CO₂ or CO becausethese gases would be expected to be reactive toward the particularreaction, process, or material around which they would surround orblanket, despite their occasional use as inert blanketing gases in otherprocesses.

The term precontacted mixture is used herein to describe a first mixtureof catalyst components that are contacted for a first period of timeprior to the first mixture being used to form a postcontacted or secondmixture of catalyst components that are contacted for a second period oftime. In one aspect of the invention, the precontacted mixture describesa mixture of metallocene, olefin or alkyne monomer, and organoaluminumcompound, before this mixture is contacted with the acidicactivator-support and optionally an organoaluminum compound. Thus,precontacted describes components that are used to contact each other,but prior to contacting the components in the second, postcontactedmixture. Accordingly, this invention may occasionally distinguishbetween a component used to prepare the precontacted mixture and thatcomponent after the mixture has been prepared. For example, according tothis description, it is possible for the precontacted organoaluminumcompound, once it is admixed with the metallocene and the olefin oralkyne monomer, to have reacted to form at least one different chemicalcompound, formulation, or structure from the distinct organoaluminumcompound used to prepare the precontacted mixture. In this case, theprecontacted organoaluminum compound or component is described ascomprising an organoaluminum compound that was used to prepare theprecontacted mixture.

Similarly, the term postcontacted mixture is used herein to describe asecond mixture of catalyst components that are contacted for a secondperiod of time, and one constituent of which is the precontacted orfirst mixture of catalyst components that were contacted for a firstperiod of time. Typically, the term postcontacted mixture is used hereinto describe the mixture of metallocene, olefin or alkyne monomer,organoaluminum compound, and acidic activator-support, formed fromcontacting the precontacted mixture of a portion of these componentswith the any additional components added to make up the postcontactedmixture. Generally, the additional component added to make up thepostcontacted mixture is the acidic activator-support, and optionallymay include an organoaluminum compound the same or different from theorganoaluminum compound used to prepare the precontacted mixture, asdescribed herein. Accordingly, this invention may also occasionallydistinguish between a component used to prepare the postcontactedmixture and that component after the mixture has been prepared.

The term metallocene is used herein to refer to metallocene andmetallocene-like compounds containing at least one η⁵-alkadienyl ligand,in one aspect at least one η⁵-cycloalkadienyl ligand, and in anotheraspect at least one η⁵-cyclopentadienyl ligand, or its analogs orderivatives. Thus, the metallocenes of this invention typically compriseat least one cyclopentadienyl, indenyl, fluorenyl, or boratabenzeneligand, or substituted derivatives thereof. Possible substituents onthese ligands include hydrogen, therefore the description “substitutedderivatives thereof” in this invention comprises partially saturatedligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like. In some contexts, themetallocene may be referred to simply as the “catalyst”, in much thesame way the term “cocatalyst” may be used herein to refer to anorganoaluminum compound.

The terms catalyst composition, catalyst mixture, and the like are usedherein to refer to either the precontacted mixture or the postcontactedmixture as the context requires. The use of these terms does not dependupon the actual product of the reaction of the components of themixtures, the nature of the active catalytic site, or the fate of thealuminum cocatalyst, metallocene compound, olefin or alkyne monomer usedto prepare the precontacted mixture, or the specific reactions of theacidic activator-support after combining these components. Therefore,the terms catalyst composition, catalyst mixture, and the like includeboth heterogeneous compositions and homogenous compositions.

The term hydrocarbyl is used to specify a hydrocarbon radical group thatincludes, but is not limited to aryl, alkyl, cycloalkyl, alkenyl,cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl,and the like, and includes all substituted, unsubstituted, branched,linear, heteroatom substituted derivatives thereof.

The terms solid acidic activator-support, acidic activator-support, orsimply activator-support, and the like are used herein to indicate atreated, solid, inorganic oxide of relatively high porosity, whichexhibits Lewis acidic or Brønsted acidic behavior, and which has beentreated with an electron-withdrawing component, typically an anion, andwhich is calcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, in one aspect, thetreated solid oxide compound comprises the calcined contact product ofat least one solid oxide compound with at least one electron-withdrawinganion source compound. In another aspect, the activator-support or“treated solid oxide compound” comprises at least one ionizing, acidicsolid oxide compound. The terms support or activator-support are notused to imply these components are inert, and this component should notbe construed as an inert component of the catalyst composition.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed above and throughout the text areprovided solely for their disclosure prior to the filing date of thepresent application. Nothing herein is to be construed as an admissionthat the inventors are not entitled to antedate such disclosure byvirtue of prior invention.

For any particular compound disclosed herein, any general structurepresented also encompasses all conformational isomers, regioisomers, andstereoisomers that may arise from a particular set of substituents. Thegeneral structure also encompasses all enantiomers, diastereomers, andother optical isomers whether in enantiomeric or racemic forms, as wellas mixtures of stereoisomers, as the context requires.

The present invention is further illustrated by the following examples,which are not to be construed in any way as imposing limitations uponthe scope thereof. On the contrary, it is to be clearly understood thatresort may be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

In the following examples, unless otherwise specified, the syntheses andpreparations described therein were carried out under an inertatmosphere such as nitrogen or argon. Solvents were purchased fromcommercial sources and were typically dried over activated alumina priorto use. Unless otherwise specified, reagents were obtained fromcommercial sources.

EXAMPLE 1 Preparation of a Fluorided Silica-Alumina AcidicActivator-Support

The silica-alumina used to prepare the fluorided silica-alumina acidicactivator-support in this Example was obtained from W. R. Grace as GradeMS13-110, containing 13% alumina, having a pore volume of about 1.2 cc/gand a surface area of about 400 m²/g. This material was fluorided byimpregnation to incipient wetness with a solution containing ammoniumbifluoride in an amount sufficient to equal 10 wt % of the weight of thesilica-alumina. This impregnated material was then dried in a vacuumoven for 8 hours at 100° C. The thus-fluorided silica-alumina sampleswere then calcined as follows. About 10 grams of the alumina were placedin a 1.75-inch quartz tube fitted with a sintered quartz disk at thebottom. While the silica was supported on the disk, dry air was blown upthrough the disk at the linear rate of about 1.6 to 1.8 standard cubicfeet per hour. An electric furnace around the quartz tube was used toincrease the temperature of the tube at the rate of about 400° C. perhour to a final temperature of about 450° C. At this temperature, thesilica-alumina was allowed to fluidize for three hours in the dry air.Afterward, the silica-alumina was collected and stored under drynitrogen, and was used without exposure to the atmosphere.

EXAMPLE 2 Preparation of a Precontacted/Postcontacted CatalystComposition and Comparison of its Polymerization Activity with aStandard Catalyst Composition

The present invention was tested in a comparative study of a catalystcomposition comprising bis(cyclopentadienyl)zirconium dichloridecatalyst, triethylaluminum (TEA), monomer (ethylene) and comonomer(1-hexene), and acidic activator-support (fluorided silica-alumina),both with and without the precontacting step of the metallocene, TEA,and 1-hexene. The data obtained in this study are provided in Table 1,using an acidic activator-support of fluorided silica alumina.

A stock solution of 45 mg of bis(cyclopentadienyl)zirconium dichloridein 45 mL of dry, degassed toluene was prepared for the experiments ofTable 1. Control Example 2A of Table 1 represents polymerization dataobtained from the near simultaneous contacting of 5 mL of thebis(cyclopentadienyl)zirconium dichloride stock solution, 200 mg offluorided silica alumina, 1 mL of 15 wt % triethylaluminum (TEA) inheptane, 20 g of comonomer (1-hexene) and monomer (ethylene), withoutextended precontacting of any catalyst components.

The polymerization reaction was carried out in a 1-gallon autoclave asfollows. Under an isobutane purge 5 mL of thebis(cyclopentadienyl)zirconium dichloride stock solution, immediatelyfollowed by 200 mg of support-activator, was charged to the autoclave.The autoclave was sealed, 2 liters of isobutane were added, along with20 g of 1-hexene and 1 mL of 15 wt % triethylaluminum (TEA) in heptane.Stirring was initiated and maintained at about 700 rpm as the reactorwas heated to 90° C. over a period of about 2 minutes. The totalpressure was brought to 550 psig with ethylene. Ethylene was fed to thereactor on demand to maintain the pressure at 550 psig. After 1 hr, thestirrer and heating were then stopped and the reactor was rapidlydepressurized. The autoclave was then opened and the solid polyethylenewas physically removed. The activity values provided in Example 2A ofTable 1 provide a baseline of catalyst and activator activity forcomparison.

Example 2B of Table 1 demonstrates that precontactingbis(cyclopentadienyl)zirconium dichloride with 1-hexene and TEA prior tocharging to the autoclave gave a catalyst that exhibited higher activitythan that of Example 2A. Thus, 5 mL of the metallocene stock solutionwas treated with 2 mL of 1-hexene and 1 mL of 15 wt % TEA in heptanes.This solution was stirred for 30 minutes prior to charging to theautoclave. This precontacted solution was then charged to the 1 gallonautoclave immediately followed by 200 mg of the activator-support. Theautoclave was then sealed and 2 L of isobutane, along with 20 g of1-hexene, were quickly added to the reactor. Stirring was initiated andmaintained at about 700 rpm as the reactor was heated to 90° C. over aperiod of about 2 minutes. The total pressure was brought to 550 psigwith ethylene. Thus, the postcontacted mixture, containing theprecontacted solution and the support activator, was allowed to remainin contact for a period of about 2 minutes prior to introducingethylene. Ethylene was fed to the reactor on demand to maintain thepressure at 550 psig. After 53 minutes, the stirrer and heating werethen stopped and the reactor was rapidly depressurized. The autoclavewas then opened and the solid polyethylene was physically removed. Thereactor had substantially no indication of any wall scale, coating orother forms of fouling following the reaction. TABLE 1 PolymerizationData Related to Precontact Time of Cp₂ZrCl₂ with TEA and 1-Hexene.Activator- Activator- Precontact Support Catalyst. Solid CatalystSupport Time Weight Weight Run Time Polymer Activity Activity Example(min) (mg) (mg) (min) (g) (g/g/hr) (g/g/hr) 2A 0 200 5 60 328.1 656181640 2B 30 200 5 53 517.9. 117260 2932

EXAMPLE 3 Comparison of the Polymerization Activity of CatalystCompositions Prepared by Varying the Components that are Precontactedand Postcontacted

In Examples 3A-3D presented in Table 2, 1 mL of a 1 mg/1 mL toluenestock solution of bis(cyclopentadienyl)zirconium dichloride wasoptionally treated, in various combinations, with 1 mL of 15 wt %triethylaluminum, 2 mL of 1-hexene, and 200 mg of a fluoridedsilica-alumina activator-support for 30 minutes before introduction ofthis mixture to the polymerization autoclave. The stock solution wasprepared under an atmosphere of nitrogen by dissolving 45 mg ofbis(cyclopentadienyl)zirconium dichloride in 45 mL of dry toluene.Polymerizations were conducted for 60 minutes in isobutane at 90° C.,550 psig of ethylene, with 20 grams of 1-hexene. A “Yes” or “No” inTable 2 indicates the presence or absence of these reagents,respectively, in the precontacted mixture in the 30 minute period priorto introduction to the autoclave.

In Example 3A, 1 mL of 1 mg/1 mL toluene stock solution ofbis(cyclopentadienyl)zirconium dichloride was treated with both 1 mL of15 wt % trialkylaluminum in heptane and 2 mL of 1-hexene, under anatmosphere of nitrogen. This precontacted mixture composition containingthese three reagents was stirred for 30 minutes before being charged tothe autoclave. This precontacted solution was then charged to the 1gallon autoclave immediately followed by 200 mg of theactivator-support. The autoclave was then sealed and 2 L of isobutane,along with 20 g of 1-hexene, were quickly added to the reactor. Stirringwas initiated and maintained at about 700 rpm as the reactor was heatedto 90° C. over a period of about 2 minutes. The total pressure wasbrought to 550 psig with ethylene. Thus, the postcontacted mixture,containing the precontacted solution and the support activator, wasallowed to remain in contact for a period of about 2 minutes prior tointroducing ethylene. Ethylene was fed to the reactor on demand tomaintain the pressure at 550 psig. After 60 minutes, the stirrer andheating were then stopped and the reactor was rapidly depressurized. Theautoclave was then opened and the solid polyethylene was physicallyremoved. The reactor had substantially no indication of any wall scale,coating or other forms of fouling following the reaction.

In Example 3B, 1 mL of the 1 mg/1 mL toluene stock solution ofbis(cyclopentadienyl)zirconium dichloride was treated only with 1 mL of15 wt % triethylaluminum in the precontacted mixture. This precontactedmixture composition containing these two reagents was stirred for 30minutes before being charged to the autoclave. This precontactedsolution was then charged to the 1 gallon autoclave immediately followedby 200 mg of the activator-support. The autoclave was then sealed and 2L of isobutane, along with 20 g of 1-hexene, were quickly added to thereactor. Stirring was initiated and maintained at about 700 rpm as thereactor was heated to 90° C. over a period of about 2 minutes. The totalpressure was brought to 550 psig with ethylene. Thus, the postcontactedmixture, containing the precontacted solution and the support activator,was allowed to remain in contact for a period of about 2 minutes priorto introducing ethylene. Ethylene was fed to the reactor on demand tomaintain the pressure at 550 psig. After 60 minutes, the stirrer andheating were then stopped and the reactor was rapidly depressurized. Theautoclave was then opened and the solid polyethylene was physicallyremoved. The reactor had substantially no indication of any wall scale,coating or other forms of fouling following the reaction. This Examplegave a lower activity than Example 3A.

In Example 3C, 1 mL of the 1 mg/1 mL toluene stock solution ofbis(cyclopentadienyl)zirconium dichloride was treated only with 2 mL of1-hexene in the pre-contacted mixture. This precontacted mixturecomposition containing these two reagents was stirred for 30 minutesbefore being charged to the autoclave. This precontacted solution wasthen charged to the 1 gallon autoclave immediately followed by 200 mg ofthe activator-support. The autoclave was then sealed and 2 L ofisobutane, along with 20 g of 1-hexene and 1 mL of 15 wt %triethylaluminum, were quickly added to the reactor. Stirring wasinitiated and maintained at about 700 rpm as the reactor was heated to90° C. over a period of about 2 minutes. The total pressure was broughtto 550 psig with ethylene. Thus, the postcontacted mixture, containingthe precontacted solution and the support activator, was allowed toremain in contact for a period of about 2 minutes prior to introducingethylene. Ethylene was fed to the reactor on demand to maintain thepressure at 550 psig. After 60 minutes, the stirrer and heating werethen stopped and the reactor was rapidly depressurized. The autoclavewas then opened and the solid polyethylene was physically removed. Thereactor had substantially no indication of any wall scale, coating orother forms of fouling following the reaction. This Example gave a loweractivity than Example 3A.

In Example 3D, 1 mL of the 1 mg/1 mL toluene stock solution ofbis(cyclopentadienyl)zirconium dichloride was treated with 2 mL of1-hexene and 200 mg of the activator-support in the pre-contactedmixture. This precontacted mixture composition containing these threereagents was stirred for 30 minutes before being charged to theautoclave. This precontacted slurry was then charged to the 1 gallonautoclave immediately followed by 200 mg of the activator-support. Theautoclave was then sealed and 2 L of isobutane, along with 20 g of1-hexene and 1 mL of 15 wt % triethylaluminum, were quickly added to thereactor. Stirring was initiated and maintained at about 700 rpm as thereactor was heated to 90° C. over a period of about 2 minutes. The totalpressure was brought to 550 psig with ethylene. Thus, the postcontactedmixture, containing the precontacted solution and the support activator,was allowed to remain in contact for a period of about 2 minutes priorto introducing ethylene. Ethylene was fed to the reactor on demand tomaintain the pressure at 550 psig. After 60 minutes, the stirrer andheating were then stopped and the reactor was rapidly depressurized. Theautoclave was then opened and the solid polyethylene was physicallyremoved. The reactor had substantially no indication of any wall scale,coating or other forms of fouling following the reaction. This Examplegave a lower activity than Example 3A. TABLE 2 Polymerization DataRelated to Components Present in the Precontacted Mixture ContainingCp₂ZrCl₂ Precontact Mixture Activator- Composition Catalyst Support 1-Activator- Solid PE Activity Activity Example TEA hexene Support (g)(g/g/hr) (g/g/hr) 3A yes yes no 309.3 309300 1547 3B yes no no 235.9235900 1180 3C no yes no 177.6 177600 888 3D no yes yes 115.6 115600 578

These experiments demonstrate the higher activity for precontacting themetallocene with both 1-hexene and TEA in the absence ofactivator-support.

EXAMPLE 4 Activity of Catalysts Derived from Various Precontacted andPostcontacted Catalyst Compositions and Study of the Presence of theActivator-Support in the Precontacted Catalyst Composition

Experiments 4A and 4B presented in Table 3 provide a comparison ofcatalyst compositions comprising the metallocene catalyst,bis(2,7-di-tert-butylfluorenyl)-ethan-1,2-diylzirconium (IV) dichloride,triethylaluminum (TEA), monomer (ethylene) and comonomer (1-hexene), andfluorided silica-alumina activator-support. A 1 mg metallocene/1 mLtoluene stock solution (6 mL) was optionally treated with 1 mL of 15 wt% triethylaluminum, 2 mL of 1-hexene, and 200 mg of fluoridedsilica-alumina activator-support for 45 minutes before introduction tothe polymerization autoclave, according to the data in Table 3. Thus, a“yes” or “no” entry in Table 3 indicates the presence of these reagentsin a 45 minute precontact step with the metallocene, prior tointroducing the precontacted mixture to the autoclave. Polymerizationswere conducted for 60 minutes in isobutane at 80° C., 450 psig ethylene,with 20 grams of 1-hexene.

In Example 4A, under an atmosphere of nitrogen, 6 mL of 1 mg/1 mLtoluene stock solution of thebis(2,7-di-tert-butylfluorenyl)-ethan-1,2-diylzirconium (IV) dichloridemetallocene was treated with both 1 mL of 15 wt % trialkylaluminum inheptane and 2 mL of 1-hexene. This precontacted mixture compositioncontaining these three reagents was stirred for 45 minutes before beingcharged to the autoclave. This precontacted solution was then charged tothe 1 gallon autoclave immediately followed by 200 mg of theactivator-support. The autoclave was then sealed and 2 L of isobutane,along with 20 g of 1-hexene, were quickly added to the reactor. Stirringwas initiated and maintained at about 700 rpm as the reactor was heatedto 80° C. over a period of about 2 minutes. The total pressure wasbrought to 450 psig with ethylene. Thus, the postcontacted mixture,containing the precontacted solution and the support activator, wasallowed to remain in contact for a period of about 2 minutes prior tointroducing ethylene. Ethylene was fed to the reactor on demand tomaintain the pressure at 450 psig. After 60 minutes, the stirrer andheating were then stopped and the reactor was rapidly depressurized. Theautoclave was then opened and the solid polyethylene was physicallyremoved. TABLE 3 Polymerization Data Related to Components andConditions Precontact Mixture Activator- Composition Catalyst Support 1-Activator- Solid PE Activity Activity Example TEA hexene Support (g)(g/g/hr) (g/g/hr) 4A yes yes no 74.3 12383 743 4B yes yes yes 31.8 5300318

In comparative Example 4B, the fluorided silica-aluminaactivator-support was present in the precontacted mixture along with thebis(2,7-di-tert-butylfluorenyl)-ethan-1,2-diylzirconium (IV) dichloridemetallocene catalyst, triethylaluminum (TEA), and hexane comonomer.Thus, 6 mL of a 1 mg/1 mL toluene stock solution of metallocene wasslurried with 1 mL of 15 wt % trialkylaluminum in heptane, 2 mL of1-hexene, and 200 mg of the activator-support. This precontacted mixturecontaining all four catalyst components was stirred for 45 minutesbefore being charged to an autoclave. The autoclave was then sealed and2 L of isobutane, along with 20 g of 1-hexene, were quickly added to thereactor. Stirring was initiated and maintained at about 700 rpm as thereactor was heated to 80° C. over a period of about 2 minutes. The totalpressure was brought to 450 psig with ethylene. Ethylene was fed to thereactor on demand to maintain the pressure at 450 psig. After 60minutes, the stirrer and heating were then stopped and the reactor wasrapidly depressurized. The autoclave was then opened and the solidpolyethylene was physically removed. As Table 3 indicates, the Example4B catalyst exhibited a lower catalyst activity than the Example 4Acatalyst.

EXAMPLE 5 Preparation of Various Precontacted and Postcontacted CatalystCompositions and Comparison of their Polymerization Activities

The Experiments presented in Table 4 provide a comparison of catalystcompositions comprising the metallocene catalyst,[η⁵-cyclopentadienyl-η⁵-(9-fluorenyl) hex-1-ene]zirconium dichloride,CH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂, triethylaluminum (TEA), monomer(ethylene) and comonomer (1-hexene), and fluorided silica-aluminaactivator-support, both with and without the precontacting step of themetallocene, TEA, and 1-hexene. The metallocene catalyst in thisexample, [(η⁵-C₅H₄)CCH₃(CH₂CH₂CH═CH₂)(η⁵-9-C₁₃H₉)]ZrCl₂, has thefollowing structure:

wherein R1 is methyl, R2 is butenyl (—CH₂CH₂CH═CH₂), and R3 is H.

Example 5A represents a standard catalytic run, that was obtained asfollows. Under a nitrogen atmosphere, 2 mL of 1-hexene, 2 mL of asolution of catalyst solution prepared from[η⁵-cyclopentadienyl-η⁵-(9-fluorenyl) hex-1-ene]zirconium dichloride,CH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂, in toluene (2 mg/mL), and 1 mL of 15wt % triethylaluminum in heptane solution were added to a Diels-Aldertube. This solution was immediately added to 250 mg ofactivator-support. Thus, Example 5A of Table 4 represents polymerizationdata obtained from the near simultaneous contacting ofCH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂, TEA, 1-hexene, and fluoridedsilica-alumina activator-support, without precontacting theansa-metallocene, triethylaluminum (TEA), and 1-hexene, and thereforeprovides a baseline for comparison with Examples 5B and 5C.

Example 5B represents a catalytic run obtained in the same manner as thestandard run of Example 5A, except that Example 5B included aprecontacting step of 0.25 hours for the metalloceneCH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂, TEA, and 1-hexene, prior tocontacting this mixture with the fluorided silica-aluminaactivator-support.

Example 5C represents a catalytic run obtained in the same manner as thestandard run of Example 5A, except that Example 5C included noprecontacting of the metallocene, TEA, and 1-hexene, but insteadincluded a “postcontacted” step (according to the definitions herein) of0.50 hours in which all components, namely the metalloceneCH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂, TEA, 1-hexene, and the fluoridedsilica-alumina activator-support were contacted prior to adding thispostcontacted mixture to the reactor. This example demonstrates that anincrease in activity is obtained by precontacting the metallocene, TEAand hexane, whereas when all the reactants are contacted prior toinitiating a polymerization run, a decrease in activity was observed.

Example 5D was prepared as follows. The metallocene catalystCH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂ (24 mg) was placed in a Diels-Aldertube and maintained in the dark by covering the tube with aluminum foil.A 12-mL sample of dry heptane (but no hexene) was added and this mixturewas stirred while 2 mL of 15 wt % triethylaluminum in heptane was added.This slurry was stirred in the dark at room temperature for about 17hours, to provide a light yellow solution. This sample was maintained inthe dark until use. Example 5D included a “postcontacting” step of 0.25hours for 2 mLs of this precontacted solution, 1 mL of 15 wt % TEA, andthe fluorided silica-alumina activator-support prior to adding to thereactor. Example 5D provides a baseline for comparison of Examples 5Eand 5F.

Example 5E was prepared as follows. The metallocene catalystCH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂ (24 mg) was placed in a Diels-Aldertube and maintained in the dark by covering the tube with aluminum foil.A 12-mL sample of 1-hexene was added and this mixture was stirred while2 mL of 15 wt % triethylaluminum in heptane was added. This slurry wasstirred in the dark at room temperature for about 17 hours, to provide adark yellow solution in which all the catalyst had dissolved. Thissample was maintained in the dark until use. This Example included a“postcontacting” step of 0.25 hours for 2 mLs of this solution, 1 mL of15 wt % TEA, and the fluorided silica-alumina activator-support prior toadding to the reactor.

Example 5F was prepared as follows. TheCH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂ metallocene catalyst (10 mg) wasplaced in a Diels-Alder tube, to which 20 mL of 1-hexene and 2 mL of 15wt % triethylaluminum in heptane were added. This mixture was maintainedin the dark and the Diels-Alder tube was put in an ultra sonic bath andsonicated for about 10 minutes. A dark yellow solution was obtained inwhich all the catalyst had dissolved. This sample was maintained in thedark until use. This Example included a “postcontacting” step of 0.25hours for 4 mLs of this solution, 1 mL of 15 wt % TEA, and the fluoridedsilica-alumina activator-support prior to adding to the reactor.Examples 5E and 5F show that a large increase in activity is obtained byprecontacting the metallocene, TEA and 1-hexene compared to Example 5D,where 1-hexene was excluded.

Polymerization reactions were carried out as follows. Following anyprecontact and postcontact steps for a particular sample, a catalystslurry (comprising metallocene, organoaluminum, olefin, andactivator-support) was added to a 1-gallon autoclave under an isobutanepurge. The autoclave was sealed, 2 liters of isobutane were added, andstirring was initiated and maintained at about 700 rpm. The reactor wasquickly heated to 80° C. over a period of about 2 minutes. A 25-g sampleof 1-hexene was forced into the reactor, and the total pressure wasbrought to 450 psig with ethylene. Ethylene was fed to the reactor ondemand to maintain the pressure at 450 psig for 1 hour. The stirrer andheating were then stopped and the reactor was rapidly depressurized. Theautoclave was then opened and the solid polyethylene was physicallyremoved. TABLE 4 Polymerization Data Related to Components andConditions Activator- Precontact Postcontact Catalyst Solid CatalystSupport Time Time Run Time Weight Polymer Productivity Activity ActivityExample (hours)¹ (hours)₂ (min) (g) (g) (g/g) (g/g/hr) (g/g/hr) 5A  0 −065 0.004 96.6 24150 22292 357 5B  0.25 0  49³ 0.004 94.5 23625 28929 4635C  0 0.5 64 0.004 46.6 11650 10922 175 5D 17⁴ 0.25⁴ 60 0.0034 80.623706 23706 322 5E 17⁵ 0.25 60 0.0034 319.7 94029 94029 1279 5F  0.17⁶0.25 65 0.0018 294.7 151128 151128 1088¹Precontact Time is defined as the contact time of the metalloceneCH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂, triethylaluminum (TEA), and1-hexene, which forms the precontacted mixture.²Postcontact Time is defined as the contact time between all fourcomponents, the metallocene CH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂,triethylaluminum (TEA), 1-hexene, and fluorided silica-aluminaactivator-support. This also represents the contact time betweenprecontacted mixture and the fluorided silica-alumina activator-support.³Because the polymerization rate was decreasing at the end of the 49minute run, the activity (g/g/hr) extrapolated to a per hour basisconstitutes an overestimate of the activity.⁴Neither the precontacted nor the postcontacted mixture contained anyolefin monomer. Thus, the precontacted mixture contains the metalloceneCH₂═CHCH₂CH₂C(CH₃)(Cp)(9-Flu)ZrCl₂, triethylaluminum (TEA), and heptane,but no 1-hexene. The postcontacted mixture contains the precontactedmixture, additional triethylaluminum (TEA), and fluoridedsilica-alumina.⁵Precontacted mixture maintained in the dark.⁶Precontacted mixture sonicated while maintaining in the dark.

In Table 4, Productivity is the g of polymer/g of catalyst producedduring that run, Catalyst Activity is the g of polymer/g ofcatalyst/unit time, and is a better comparison among runs, andActivator-Support Activity is the g of polymer/g ofactivator-support/unit time.

EXAMPLE 6 Larger Scale Production of Polyethylene Resin Using thePrecontacted/Postcontacted Catalyst Composition

In this Example, the pretreated metallocene catalyst of the presentinvention was used in the experimental production of 0.931 density(specification range 0.930 to 0.933) polyethylene resin to demonstratethe capability of the catalyst system to produce polyethylene polymer inlarger scale production.

Ethylene polymers were prepared in a continuous particle form process(also known as a slurry process) by contacting a catalyst with a monomerand optionally one or more α-olefin comonomers, such as 1-hexene. Themedium and temperature are thus selected such that the copolymer isproduced as solid particles and is recovered in that form. Ethylene thathad been dried over activated alumina and/or molecular sieves was usedas the monomer. Isobutane that had been degassed by fractionation anddried over alumina and/or molecular sieves was used as the diluent.

The reactor was a liquid-full 22.5-inch inside diameter pipe loop havinga volume of 27,000 gallons. Liquid isobutane was used as the diluent,and the reactor pressure was about 600 psig. The loop reactor wasequipped with continuous take-off (CTO) and settling leg producttake-off (PTO), which can be operated in combination. The slurrydischarge of polymer and isobutane along with unreacted ethylene and1-hexene from the reactor went though a heated flashline into a lowpressure flash tank and through a purge column to remove residualhydrocarbons. To prevent static buildup in the reactor, a small amount(<5 ppm of diluent) of a commercial antistatic agent sold as Stadis 450was added.

The catalyst system comprised the following components. The metallocenebis(indenyl)zirconium dichloride (η⁵-C₉H₇)₂ZrCl₂, 1-hexene diluent, andtriethylaluminum (TEA) were precontacted for a period of about 9 days ina first premixing pot, prior to being introduced into a second“premixing” vessel. After this time, the metallocene-olefin-TEA mixtureconstituting one feed, the activator-support slurried in isobutaneconstituting a second feed, and additional triethylaluminum (TEA) inisobutane constituting a third feed were introduced into the second“premixing” vessel to form the postcontacted mixture, according thisinvention, before introduction into the loop reactor. Once introduced inthis second premixing vessel to form the postcontacted mixture, thismixture was stirred with a residence time of approximately 28 minutes,prior to introduction into the loop reactor.

The metallocene bis(indenyl)zirconium dichloride concentration wasapproximately 1 part per million of the reactor concentration. The totalTEA added was approximately 10 part per million of the reactorconcentration. The solid activator-support component, was dehydrated ina fluidized bed at 950° F. to 1000° F., then charged to the conventionalcatalyst metering vessel used for chromium catalyst and metered througha 35 or 49-cc feeder into the second premixing vessel.

Typical and approximate reactor conditions for this experimental runwere: 190° F. reactor temperature, 5.5 to 7.0 weight percent ethylenemeasured in the off-gas from the low pressure flash chamber via on-linegas chromatography, 3.5 to 4.5 weight percent 1-hexene measured in theoff-gas from the low pressure flash chamber via on-line gaschromatography, no hydrogen, and reactor solids up to 38 weight percent.

The reactor was operated to have a residence time of 45 minutes to 1.5hours. At steady state conditions, the isobutane feed rate was about30,000 to 36,000 pounds per hour, the ethylene feed rate was about30,000 to 34,000 pounds per hour, and the 1-hexene feed rate was variedto control the density of the polymer product. Ethylene concentration inthe diluent was 5 to 7 weight percent. Catalyst concentrations in thereactor can be such that the catalyst system content ranges from 0.001to about 1 weight percent based on the weight of the reactor contents.Polymer was removed from the reactor at the rate of about 33,000 to37,000 pounds per hour and recovered in a flash chamber.

1. A catalyst composition comprising: at least one precontactedmetallocene; at least one precontacted organoaluminum compound; at leastone precontacted olefin or alkyne; and at least one postcontacted acidicactivator-support.
 2. The catalyst composition of claim 1, wherein thepostcontacted acidic activator-support comprises a solid oxide treatedwith an electron-withdrawing anion, wherein: the solid oxide is selectedfrom silica, alumina, silica-alumina, aluminum phosphate,heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide,mixed oxides thereof, or mixtures thereof; and the electron-withdrawinganion is selected from fluoride, chloride, bromide, phosphate, triflate,bisulfate, sulfate, or any combination thereof.
 3. The catalystcomposition of claim 1, wherein the postcontacted acidicactivator-support comprises fluorided silica-alumina.
 4. The catalystcomposition of claim 3 wherein the fluorided silica-alumina comprisesfrom about 5% to about 95% by weight alumina and from about 2% to about50% by weight fluoride ion, based on the weight of the fluoridedsilica-alumina after drying but before calcining.
 5. The catalystcomposition of claim 3, wherein the fluorided silica-alumina comprisessilica-alumina having a pore volume greater than about 0.5 cc/g, and asurface area greater than about 100 m²/g.
 6. The catalyst composition ofclaim 1, wherein the precontacted metallocene comprises a compoundhaving the following formula:(X¹)(X²)(X³)(X⁴)M¹, wherein M¹ is selected from titanium, zirconium, orhafnium; wherein (X¹) is independently selected from cyclopentadienyl,indenyl, fluorenyl, boratabenzene, substituted cyclopentadienyl,substituted indenyl, substituted fluorenyl, or substitutedboratabenzene; wherein each substituent on the substitutedcyclopentadienyl, substituted indenyl, substituted fluorenyl orsubstituted boratabenzene of (X¹) is independently selected from analiphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogengroup, a phosphorus group, an arsenic group, a carbon group, a silicongroup, a germanium group, a tin group, a lead group, a boron group, analuminum group, an inorganic group, an organometallic group, or asubstituted derivative thereof, any one of which having from 1 to about20 carbon atoms; a halide; or hydrogen; wherein at least one substituenton (X¹) is optionally a bridging group that connects (X¹) and (X²);wherein (X³) and (X⁴) are independently selected from an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, agermanium group, a tin group, a lead group, a boron group, an aluminumgroup, an inorganic group, an organometallic group, or a substitutedderivative thereof, any one of which having from 1 to about 20 carbonatoms; or a halide. wherein (X²) is independently selected from acyclopentadienyl group, an indenyl group, a fluorenyl group, aboratabenzene group, an aliphatic group, an aromatic group, a cyclicgroup, a combination of aliphatic and cyclic groups, an oxygen group, asulfur group, a nitrogen group, a phosphorus group, an arsenic group, acarbon group, a silicon group, a germanium group, a tin group, a leadgroup, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide; wherein eachsubstituent on the substituted (X²) is independently selected from analiphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogengroup, a phosphorus group, an arsenic group, a carbon group, a silicongroup, a germanium group, a tin group, a lead group, a boron group, analuminum group, an inorganic group, an organometallic group, or asubstituted derivative thereof, any one of which having from 1 to about20 carbon atoms; a halide; or hydrogen; and wherein at least onesubstituent on (X²) is optionally a bridging group that connects (X¹)and (X²).
 7. The catalyst composition of claim 1, wherein theprecontacted metallocene comprises a metallocene compound selected from:bis(cyclopentadienyl)hafnium dichloride; bis(cyclopentadienyl)zirconiumdichloride; 1,2-ethanediylbis(η⁵-1-indenyl)di-n-butoxyhafnium;1,2-ethanediylbis(η⁵-1-indenyl)dimethylzirconium;3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride;methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride; bis(n-butylcyclopentadienyl)bis(t-butylamido)hafnium;bis(1-n-butyl-3-methyl-cyclopentadienyl)zirconium dichloride;bis(n-butylcyclopentadienyl)zirconium dichloride;dimethylsilylbis(1-indenyl)zirconium dichloride;octylphenylsilylbis(1-indenyl)hafnium dichloride;dimethylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride;dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride;1,2-ethanediylbis(9-fluorenyl)zirconium dichloride; indenyl diethoxytitanium(IV) chloride;(isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride;bis(pentamethylcyclopentadienyl)zirconium dichloride;bis(indenyl)zirconium dichloride;methyloctylsilylbis(9-fluorenyl)zirconium dichloride;bis(2,7-di-tert-butylfluorenyl)-ethan-1,2-diyl)zirconium(IV) dichloride;bis-[1-(N,N-diisopropylamino)boratabenzene]hydridozirconiumtrifluoromethylsulfonate;methyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride;methyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride;methyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride;methyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride;phenyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride;phenyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride;phenyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride; orphenyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride.
 8. The catalyst composition of claim 1, wherein theprecontacted organoaluminum compound comprises an organoaluminumcompound with the following formula:Al(X⁵)_(n)(X⁶)_(3−n), wherein (X⁵) is a hydrocarbyl having from 2 toabout 20 carbon atoms; (X⁶) is selected from alkoxide or aryloxide, anyone of which having from 1 to about 20 carbon atoms, halide, or hydride;and n is a number from 1 to 3, inclusive.
 9. The catalyst composition ofclaim 1, wherein the precontacted organoaluminum compound comprisestriethylaluminum (TEA), tripropylaluminum, diethylaluminum ethoxide,tributylaluminum, disobutylaluminum hydride, triisobutylaluminum,diethylaluminum chloride, or combinations thereof.
 10. The catalystcomposition of claim 1, further comprising at least one postcontactedorganoaluminum compound with the following formula:Al(X⁵)_(n)(X⁶)_(3−n), wherein (X⁵) is a hydrocarbyl having from 1 toabout 20 carbon atoms; (X⁶) is selected from alkoxide or aryloxide, anyone of which having from 1 to about 20 carbon atoms, halide, or hydride;and n is a number from 1 to 3, inclusive.
 11. The catalyst compositionof claim 1, wherein the precontacted olefin or alkyne comprises acompound having from 2 to about 30 carbon atoms per molecule and havingat least one carbon-carbon double bond or at least one carbon-carbontriple bond.
 12. The catalyst composition of claim 1, wherein theprecontacted metallocene comprises bis(indenyl)zirconium dichloride,bis(cyclopentadienyl)zirconium dichloride, orbis(2,7-di-tert-butylfluorenyl)-ethan-1,2-diyl)zirconium (IV)dichloride; the precontacted organoaluminum compound comprisestriethylaluminum; the precontacted olefin comprises 1-hexene; and thepostcontacted acidic activator-support comprises fluoridedsilica-alumina.
 13. The catalyst composition of claim 1, wherein theprecontacted organoaluminum compound comprises an aluminacyclopentane,an aluminacyclopentadiene, or an aluminacyclopentene.
 14. The catalystcomposition of claim 1, wherein the mole ratio of the metallocene to theorganoaluminum compound is from about 1:1 to about 1:10,000.
 15. Thecatalyst composition of claim 1, wherein the mole ratio of the olefin oralkyne to the metallocene in the precontacted mixture is from about 1:10to about 100,000:1.
 16. The catalyst composition of claim 1, wherein theweight ratio of the metallocene to the acidic activator-support is fromabout 1:1 to about 1:1,000,000.
 17. The catalyst composition of claim 1,wherein the weight ratio of the acidic activator-support to theorganoaluminum compound is from about 1:5 to about 1000:1.
 18. Thecatalyst composition of claim 1, wherein the precontacted metallocenecomprises a compound with the formula I:

wherein E is selected from C, Si, Ge, or Sn; R1 is selected from H or ahydrocarbyl group having from 1 to about 12 carbon atoms; R2 is selectedfrom an alkenyl group having from about 3 to about 12 carbon atoms; andR3 is selected from H or a hydrocarbyl group having from 1 to about 12carbon atoms.
 19. The catalyst composition of claim 1, wherein theprecontacted metallocene comprises a compound with the formula II:

wherein R1 is selected from methyl or phenyl; R2 is selected from3-butenyl (—CH₂CH₂CH═CH₂) or 4-pentenyl (—CH₂CH₂CH₂CH═CH₂); and R3 isselected from H or t-butyl.
 20. A process to produce a catalystcomposition, comprising: contacting at least one metallocene, at leastone organoaluminum compound, and at least one olefin or alkyne for afirst period of time to form a precontacted mixture comprising at leastone precontacted metallocene, at least one precontacted organoaluminumcompound, and at least one precontacted olefin or alkyne; and contactingthe precontacted mixture with at least one acidic activator-support fora second period of time to form a postcontacted mixture comprising atleast one postcontacted metallocene, at least one postcontactedorganoaluminum compound, at least one postcontacted olefin or alkyne,and at least one postcontacted acidic activator-support.
 21. The processof claim 20, wherein the metallocene, the organoaluminum compound, andthe olefin or alkyne are precontacted for a first period of time fromabout 1 minute to about 9 days in the precontacted mixture.
 22. Theprocess of claim 20, wherein the precontacted mixture and the acidicactivator-support are contacted for a second period of time from about 1minute to about 24 hours in the postcontacted mixture.
 23. The processof claim 20, wherein the precontacted metallocene comprises ametallocene compound with the following formula:(X¹)(X²)(X³)(X⁴)M¹, wherein M¹ is selected from titanium, zirconium, orhafnium; wherein (X¹) is independently selected from cyclopentadienyl,indenyl, fluorenyl, boratabenzene, substituted cyclopentadienyl,substituted indenyl, substituted fluorenyl, or substitutedboratabenzene; wherein each substituent on the substitutedcyclopentadienyl, substituted indenyl, substituted fluorenyl orsubstituted boratabenzene of (X¹) is independently selected from analiphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogengroup, a phosphorus group, an arsenic group, a carbon group, a silicongroup, a germanium group, a tin group, a lead group, a boron group, analuminum group, an inorganic group, an organometallic group, or asubstituted derivative thereof, any one of which having from 1 to about20 carbon atoms; a halide; or hydrogen; wherein at least one substituenton (X¹) is optionally a bridging group that connects (X¹) and (X²);wherein (X³) and (X⁴) are independently selected from an aliphaticgroup, an aromatic group, a cyclic group, a combination of aliphatic andcyclic groups, an oxygen group, a sulfur group, a nitrogen group, aphosphorus group, an arsenic group, a carbon group, a silicon group, agermanium group, a tin group, a lead group, a boron group, an aluminumgroup, an inorganic group, an organometallic group, or a substitutedderivative thereof, any one of which having from 1 to about 20 carbonatoms; or a halide. wherein (X²) is independently selected from acyclopentadienyl group, an indenyl group, a fluorenyl group, aboratabenzene group, an aliphatic group, an aromatic group, a cyclicgroup, a combination of aliphatic and cyclic groups, an oxygen group, asulfur group, a nitrogen group, a phosphorus group, an arsenic group, acarbon group, a silicon group, a germanium group, a tin group, a leadgroup, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide; wherein eachsubstituent on the substituted (X²) is independently selected from analiphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogengroup, a phosphorus group, an arsenic group, a carbon group, a silicongroup, a germanium group, a tin group, a lead group, a boron group, analuminum group, an inorganic group, an organometallic group, or asubstituted derivative thereof, any one of which having from 1 to about20 carbon atoms; a halide; or hydrogen; and wherein at least onesubstituent on (X²) is optionally a bridging group that connects (X¹)and (X²).
 24. The process of claim 20, wherein the precontactedmetallocene comprises a metallocene compound selected from:bis(cyclopentadienyl)hafnium dichloride; bis(cyclopentadienyl)zirconiumdichloride; 1,2-ethanediylbis(η⁵-1-indenyl)di-n-butoxyhafnium;1,2-ethanediylbis(η⁵-1-indenyl)dimethylzirconium;3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride;methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride; bis(n-butylcyclopentadienyl)bis(t-butylamido)hafnium;bis(1-n-butyl-3-methyl-cyclopentadienyl)zirconium dichloride;bis(n-butylcyclopentadienyl)zirconium dichloride;dimethylsilylbis(1-indenyl)zirconium dichloride;octylphenylsilylbis(1-indenyl)hafnium dichloride;dimethylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride;dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride;1,2-ethanediylbis(9-fluorenyl)zirconium dichloride; indenyl diethoxytitanium(IV) chloride;(isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride;bis(pentamethylcyclopentadienyl)zirconium dichloride;bis(indenyl)zirconium dichloride;methyloctylsilylbis(9-fluorenyl)zirconium dichloride;bis(2,7-di-tert-butylfluorenyl)-ethan-1,2-diyl)zirconium (IV)dichloride; orbis-[1-(N,N-diisopropylamino)boratabenzene]hydridozirconiumtrifluoromethylsulfonate;methyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride;methyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride;methyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride;methyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride;phenyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride;phenyl-3-butenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride;phenyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-9-fluorenyl)zirconiumdichloride; orphenyl-4-pentenylmethylidene(η⁵-cyclopentadienyl)(η⁵-2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride.
 25. The process of claim 20, wherein the precontactedorganoaluminum compound comprises an organoaluminum compound with thefollowing formula:Al(X⁵)_(n)(X⁶)_(3−n), wherein (X⁵) is a hydrocarbyl having from 2 toabout 20 carbon atoms; (X⁶) is selected from alkoxide or aryloxide, anyone of which having from 1 to about 20 carbon atoms, halide, or hydride;and n is a number from 1 to 3, inclusive.
 26. The process of claim 20,wherein the precontacted organoaluminum compound comprisestriethylaluminum (TEA), tripropylaluminum, diethylaluminum ethoxide,tributylaluminum, disobutylaluminum hydride, triisobutylaluminum,diethylaluminum chloride, or combinations thereof.
 27. The process ofclaim 20, further comprising contacting the precontacted mixture and theacidic activator-support with at least one postcontacted organoaluminumcompound with the following formula:Al(X⁵)_(n)(X⁶)_(3−n), wherein (X⁵) is a hydrocarbyl having from 1 toabout 20 carbon atoms; (X⁶) is selected from alkoxide or aryloxide, anyone of which having from 1 to about 20 carbon atoms, halide, or hydride;and n is a number from 1 to 3, inclusive, for a second period of time,to form a postcontacted mixture comprising at least one postcontactedmetallocene, at least one postcontacted organoaluminum compound, atleast one postcontacted olefin or alkyne, and at least one postcontactedacidic activator-support.
 28. The process of claim 20, wherein theprecontacted olefin or alkyne comprises a compound having from 2 toabout 30 carbon atoms per molecule and having at least one carbon-carbondouble bond or at least one carbon-carbon triple bond.
 29. The processof claim 20, wherein the postcontacted acidic activator-supportcomprises a solid oxide selected from silica, alumina, titania,zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixturesthereof, wherein the inorganic oxide has been treated with anelectron-withdrawing anion comprising fluoride, chloride, bromide,phosphate, triflate, bisulfate, sulfate, or combinations thereof. 30.The process of claim 20, wherein the postcontacted acidicactivator-support comprises fluorided silica-alumina.
 31. The process ofclaim 30, wherein the fluorided silica-alumina comprises from about 5%to about 95% by weight alumina and from about 2% to about 50% by weightfluoride ion, based on the weight of the fluorided silica-alumina afterdrying but before calcining.
 32. The process of claim 30, wherein thefluorided silica-alumina comprises silica-alumina having a pore volumegreater than about 0.5 cc/g, and a surface area greater than about 100m²/g.
 33. The process of claim 20, wherein the precontacted metallocenecomprises bis(indenyl)zirconium dichloride,bis(cyclopentadienyl)zirconium dichloride, orbis(2,7-di-tert-butylfluorenyl)-ethan-1,2-diyl)zirconium (IV)dichloride; the precontacted organoaluminum compound comprisestriethylaluminum; the precontacted olefin comprises 1-hexene; and thepostcontacted acidic activator-support comprises fluoridedsilica-alumina.
 34. The process of claim 20, wherein the precontactedorganoaluminum compound comprises an aluminacyclopentane, analuminacyclopentadiene, an aluminacyclopentene, or any combinationthereof.
 35. A catalyst composition comprising: at least oneprecontacted metallocene; at least one precontacted olefin or alkyne; atleast one postcontacted acidic activator-support; and at least onealuminacyclopentane.
 36. A catalyst composition comprising: at least oneprecontacted metallocene; at least one precontacted olefin or alkyne; atleast one postcontacted acidic activator-support; and at least onemetallacyclopentane of a metallocene.